Processes for polymeric precursors for caigas aluminum-containing photovoltaics

ABSTRACT

This invention relates to processes for compounds, polymeric compounds, and compositions used to prepare semiconductor and optoelectronic materials and devices including thin film and band gap materials. This invention provides a range of compounds, polymeric compounds, compositions, materials and methods directed ultimately toward photovoltaic applications, transparent conductive materials, as well as devices and systems for energy conversion, including solar cells. In particular, this invention relates to polymeric precursor compounds and precursor materials for preparing photovoltaic layers. In particular, this invention relates to molecular precursor compounds and precursor materials for preparing photovoltaic layers including CAIGAS.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of prior U.S. application Ser. No.12/848,968, filed Aug. 2, 2010, which claims the benefit of U.S.Provisional Application No. 61/231,158, filed Aug. 4, 2009, U.S.Provisional Application No. 61/302,095, filed Feb. 6, 2010, U.S.Provisional Application No. 61/302,094, filed Feb. 6, 2010, U.S.Provisional Application No. 61/326,540, filed Apr. 21, 2010, U.S.Provisional Application No. 61/333,689, filed May 11, 2010, and U.S.Provisional Application No. 61/359,228, filed Jun. 28, 2010, each ofwhich is hereby incorporated by reference in its entirety.

BACKGROUND

The development of photovoltaic devices such as solar cells is importantfor providing a renewable source of energy and many other uses. Thedemand for power is ever-rising as the human population increases. Inmany geographic areas, solar cells may be the only way to meet thedemand for power. The total energy from solar light impinging on theearth for one hour is about 4×10²⁰ joules. It has been estimated thatone hour of total solar energy is as much energy as is used worldwidefor an entire year. Thus, billions of square meters of efficient solarcell devices will be needed.

Photovoltaic devices are made by a variety of processes in which layersof semiconducting material are created on a substrate. Layers ofadditional materials are used to protect the photovoltaic semiconductorlayers and to conduct electrical energy out of the device. Thus, theusefulness of an optoelectronic or solar cell product is in generallimited by the nature and quality of the photovoltaic layers.

For example, one way to produce a solar cell product involves depositinga thin, light-absorbing, solid layer of the material copper indiumgallium diselenide, known as “CIGS,” on a substrate. A solar cell havinga thin film CIGS layer can provide low to moderate efficiency forconversion of sunlight to electricity. The CIGS layer can be made byprocessing at relatively high temperatures several elemental sourcescontaining the atoms needed for CIGS. In general, CIGS materials arecomplex, having many possible solid phases.

The CIGS elemental sources must be formed or deposited, eitherindividually or as a mixture, in a thin, uniform layer on the substrate.For example, deposition of the CIGS sources can be done as aco-deposition, or as a multistep deposition. The difficulties with theseapproaches include lack of uniformity of the CIGS layers, such as theappearance of different solid phases, imperfections in crystallineparticles, voids, cracks, and other defects in the layers.

For example, some methods for solar cells are disclosed in U.S. Pat.Nos. 5,441,897, 5,976,614, 6,518,086, 5,436,204, 5,981,868, 7,179,677,7,259,322, U.S. Patent Publication No. 2009/0280598, and PCTInternational Application Publication Nos. WO2008057119 andWO2008063190.

A significant problem is the inability in general to precisely controlthe stoichiometric ratios of the metal atoms in the layers. Manysemiconductor and optoelectronic applications are highly dependent onthe ratios of certain metal atoms in the material. Without directcontrol over those stoichiometric ratios, processes to makesemiconductor and optoelectronic materials are often less efficient andless successful in achieving desired compositions and properties. Forexample, no molecule is currently known that can be used alone, withoutother compounds, to readily prepare a layer from which CIGS materials ofany arbitrary stoichiometry can be made. Compounds or compositions thatcan fulfill this goal have long been needed.

A further difficulty is the need to heat the substrate to hightemperatures to finish the film. This can cause unwanted defects due torapid chemical or physical transformation of the layers. Hightemperatures may also limit the nature of the substrate that can beused. For example, it is desirable to make thin film photovoltaic layerson a flexible substrate such as a polymer or plastic that can be formedinto a roll for processing and installation on a building or outdoorstructure. Polymer substrates may not be compatible with the hightemperatures needed to process the semiconductor layers. Preparing thinfilm photovoltaic layers on a flexible substrate is an important goalfor providing renewable solar energy and developing new generations ofelectro-optical products.

Moreover, methods for large scale manufacturing of CIGS and related thinfilm solar cells can be difficult because of the chemical processesinvolved. In general, large scale processes for solar cells areunpredictable because of the difficulty in controlling numerous chemicaland physical parameters involved in forming an absorber layer ofsuitable quality on a substrate, as well as forming the other layersrequired to make an efficient solar cell and provide electricalconductivity.

What is needed are compounds, compositions and processes to producematerials for photovoltaic layers, especially thin film layers for solarcell devices and other products.

BRIEF SUMMARY

This invention relates to compounds and compositions used to preparesemiconductor and optoelectronic materials and devices including thinfilm and band gap materials. This invention provides a range ofcompounds, compositions, materials and methods directed ultimatelytoward photovoltaic applications and other semiconductor materials, aswell as devices and systems for energy conversion, including solarcells. In particular, this invention relates to novel processes,compounds and materials for preparing semiconductor materials including(Cu,Ag)(In,Ga,Al)(S,Se) or CAIGAS materials.

This invention provides a range of compounds, compositions, materialsand methods for preparing semiconductors and materials, as well asoptoelectronic devices and photovoltaic layers. Among other things, thisdisclosure provides precursor molecules and compositions for making andusing semiconductors such as for photovoltaic layers, solar cells andother uses. In particular, this invention encompasses compounds andcompositions containing a combination of the elements copper, silver,indium, gallium, aluminum, selenium, and sulfur, including(Cu,Ag)(In,Ga,Al)(S,Se) or CAIGAS, which are useful for thin film solarcells and other uses.

In some embodiments, this invention includes polymeric precursorcompounds and compositions for preparing semiconductors, optoelectronicdevices and photovoltaic layers.

The compounds and compositions of this disclosure are stable andadvantageously allow control of the stoichiometry of the atoms inproduct materials.

In various embodiments of this invention, chemically and physicallyuniform semiconductor layers can be prepared with the polymericprecursor compounds described herein.

In further embodiments, solar cells and other products can be made inprocesses operating at relatively low temperatures with the compoundsand compositions of this disclosure.

The polymeric precursor compounds and compositions of this disclosurecan provide enhanced processability for solar cell production, and theability to be processed on a variety of substrates including polymers atrelatively low temperatures.

The advantages provided by the compounds, compositions, and materials ofthis invention in making photovoltaic layers and other semiconductorsand devices are generally obtained regardless of the morphology orarchitecture of the semiconductors or devices.

This invention includes compounds having repeating units {M^(B)(ER)(ER)}and {M^(A)(ER)(ER)}, wherein each M^(A) is Cu or Ag, each M^(B) is In,Ga or Al, each E is S, Se, or Te, and R is independently selected, foreach occurrence, from alkyl, aryl, heteroaryl, alkenyl, amido, silyl,and inorganic and organic ligands. The compounds of this disclosure maybe CAIGAS, AIGAS or CIGAS precursor compounds.

A compound of this disclosure may have the empirical formula(Cu_(1−x)Ag_(x))_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)((S_(1−z)Se_(z))R)_(w),wherein x is from 0 to 1, y is from 0 to 1, t is from 0 to 1, the sum ofy plus t is from 0 to 1, z is from 0 to 1, u is from 0.5 to 1.5, v isfrom 0.5 to 1.5, w is from 2 to 6, and R represents R groups, of whichthere are w in number, which are independently selected from alkyl,aryl, heteroaryl, alkenyl, amido, silyl, and inorganic and organicligands. A compound of this disclosure may be deficient or enriched in aGroup 11 atom.

In some aspects, a compound of this invention may be an inorganicpolymer or coordination polymer, which can be linear, branched, cyclic,or a mixture of any of the foregoing. A compound of this invention maybe an oil at a temperature below about 100° C.

In some embodiments, a compound of this invention can have three or morerepeating units {M^(B)(ER)(ER)}, or three or more repeating units{M^(A)(ER)(ER)}. In further aspects, a compound may have the formula(AB)_(n), wherein A is the repeat unit {M^(A)(ER)(ER)}, B is the repeatunit {M^(B)(ER)(ER)}, n is one or more, or n is two or more, or n isthree or more, and R is independently selected, for each occurrence,from alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganic andorganic ligands. A compound may be an alternating copolymer, a blockcopolymer, or a random copolymer.

Embodiments of this invention may further provide an ink containing oneor more polymeric precursor compounds and one or more carriers. The inkmay be a solution of the compounds in an organic carrier, or a slurry orsuspension of the compounds in an organic carrier. An ink of thisdisclosure may further contain a dopant or alkali dopant, or anadditional indium-containing compound, an additional gallium-containingcompound, or a molybdenum-containing compound, as well as one or morecomponents selected from the group of a surfactant, a dispersant, anemulsifier, an anti-foaming agent, a dryer, a filler, a resin binder, athickener, a viscosity modifier, an anti-oxidant, a flow agent, aplasticizer, a conductivity agent, a crystallization promoter, anextender, a film conditioner, an adhesion promoter, and a dye.

This invention includes methods for making a precursor compoundcomprising: a) providing monomer compounds M^(B1)(ER)³, M^(B2)(ER)₃,M^(B3)(ER)₃, M^(A1)(ER) and M^(A2)(ER); and b) contacting the monomercompounds; wherein M^(B1) is In, M^(B2) is Ga, M^(B3) is A¹, M^(A1) isCu, and M^(A2) is Ag, each E is S, Se, or Te, and each R isindependently selected, for each occurrence, from alkyl, aryl,heteroaryl, alkenyl, amido, silyl, and inorganic and organic ligands.The compound may be a CAIGAS, AIGAS or CIGAS precursor compound. In someembodiments, the monomer compounds may be contacted in a process ofdepositing, spraying, coating, or printing.

This invention includes compounds made by a process comprising reactingmonomers M^(B1)(ER)₃, M^(B2)(ER)₃, M^(B3)(ER)₃, M^(A1)(ER) andM^(A2)(ER), wherein M^(B1) is In, M^(B2) is Ga, M^(B3) is A¹, M^(A1) isCu, and M^(A2) is Ag, each E is S, Se, or Te, and R is independentlyselected, for each occurrence, from alkyl, aryl, heteroaryl, alkenyl,amido, silyl, and inorganic and organic ligands.

In further aspects, this invention includes articles comprising one ormore compounds or inks deposited onto a substrate. An article may bedeposited by spraying, spray coating, spray deposition, spray pyrolysis,printing, printing, screen printing, inkjet printing, aerosol jetprinting, ink printing, jet printing, stamp/pad printing, transferprinting, pad printing, flexographic printing, gravure printing, contactprinting, reverse printing, thermal printing, lithography,electrophotographic printing, electrodepositing, electroplating,electroless plating, bath deposition, coating, wet coating, spincoating, knife coating, roller coating, rod coating, slot die coating,meyerbar coating, lip direct coating, capillary coating, liquiddeposition, solution deposition, layer-by-layer deposition, spincasting, solution casting, and combinations of any of the forgoing.

An article may include a substrate selected from a semiconductor, adoped semiconductor, silicon, gallium arsenide, insulators, glass,molybdenum glass, silicon dioxide, titanium dioxide, zinc oxide, siliconnitride, a metal, a metal foil, molybdenum, aluminum, beryllium,cadmium, cerium, chromium, cobalt, copper, gallium, gold, lead,manganese, molybdenum, nickel, palladium, platinum, rhenium, rhodium,silver, stainless steel, steel, iron, strontium, tin, titanium,tungsten, zinc, zirconium, a metal alloy, a metal silicide, a metalcarbide, a polymer, a plastic, a conductive polymer, a copolymer, apolymer blend, a polyethylene terephthalate, a polycarbonate, apolyester, a polyester film, a mylar, a polyvinyl fluoride,polyvinylidene fluoride, a polyethylene, a polyetherimide, apolyethersulfone, a polyetherketone, a polyimide, a polyvinylchloride,an acrylonitrile butadiene styrene polymer, a silicone, an epoxy, paper,coated paper, and combinations of any of the forgoing. A substrate maybe a shaped substrate including a tube, a cylinder, a roller, a rod, apin, a shaft, a plane, a plate, a blade, a vane, a curved surface or aspheroid.

This invention may further provide methods for making an article by (a)providing one or more compounds or inks; (b) providing a substrate; and(c) depositing the compounds or inks onto the substrate. In someembodiments, step (c) can be repeated. A method may include heating thesubstrate at a temperature of from about 100° C. to about 400° C. toconvert the compounds or inks to a material, which can be followed byrepeating step (c). A method can include annealing the material byheating the substrate at a temperature of from about 300° C. to about650° C. In certain embodiments, a method includes heating the substrateat a temperature of from about 100° C. to about 400° C. to convert thecompounds or inks to a material, and annealing the material by heatingthe substrate at a temperature of from about 300° C. to about 650° C. Infurther embodiments, a method includes heating the substrate at atemperature of from about 100° C. to about 400° C. to convert thecompounds or inks to a material, depositing the compounds or inks ontothe substrate, and annealing the material by heating the substrate at atemperature of from about 300° C. to about 650° C. Additional steps of amethod can include (d) heating the substrate at a temperature of fromabout 100° C. to about 400° C. to convert the compounds or inks to amaterial; (e) depositing the compounds or inks onto the substrate; (f)repeating steps (d) and (e); and (g) annealing the material by heatingthe substrate at a temperature of from about 300° C. to about 650° C.Further embodiments include (d) heating the substrate at a temperatureof from about 100° C. to about 400° C. to convert the compounds or inksto a material; (e) annealing the semiconductor material by heating thesubstrate at a temperature of from about 300° C. to about 650° C.; and(f) repeating steps (c), (d) and (e). The methods of this invention mayfurther include an optional step of selenization or sulfurization,either before, during or after any step of heating or annealing.

In some aspects, this invention provides a material having the empiricalformula(Cu_(1−x)Ag_(x))_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)(S_(1−z)Se_(z))_(w),where x is from 0 to 1, y is from 0 to 1, t is from 0.001 to 1, the sumof y plus t is from 0.001 to 1, z is from 0 to 1, u is from 0.5 to 1.5,v is from 0.5 to 1.5, and w is from 1 to 3. The material may be asemiconductor or a thin film, and can be used to make an optoelectronicdevice.

Embodiments of this invention include methods for making a materialcomprising, (a) providing one or more compounds or inks; (b) providing asubstrate; (c) depositing the compounds or inks onto the substrate; and(d) heating the substrate at a temperature of from about 20° C. to about650° C. in an inert atmosphere, thereby producing a material having athickness of from 0.001 to 100 micrometers.

In some variations, this invention includes a thin film material made bya process comprising, (a) providing one or more compounds or inks; (b)providing a substrate; (c) depositing the compounds or inks onto thesubstrate; and (d) heating the substrate at a temperature of from about20° C. to about 650° C. in an inert atmosphere, thereby producing a thinfilm material having a thickness of from 0.001 to 100 micrometers. Aphotovoltaic absorber or device can be made with a thin film material ofthis disclosure.

In some embodiments, a photovoltaic absorber of this invention may havethe empirical formula(Cu_(1−x)Ag_(x))_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)(S_(1−z)Se_(z))_(w),where x is from 0 to 1, y is from 0 to 1, t is from 0.001 to 1, the sumof y plus t is from 0.001 to 1, z is from 0 to 1, u is from 0.5 to 1.5,v is from 0.5 to 1.5, and w is from 1 to 3. A photovoltaic device orsystem for providing electrical power may be made with a photovoltaicabsorber of this disclosure. This invention contemplates a method forproviding electrical power using a photovoltaic system to convert lightinto electrical energy.

In some aspects, this disclosure provides methods for making aphotovoltaic absorber layer on a substrate comprising, (a) providing oneor more compounds or inks;

-   (b) providing a substrate; (c) depositing the compounds or inks onto    the substrate; and (d) heating the substrate at a temperature of    from about 100° C. to about 650° C. in an inert atmosphere, thereby    producing a photovoltaic absorber layer having a thickness of from    0.001 to 100 micrometers.

This brief summary, taken along with the detailed description of theinvention, as well as the figures, the appended examples and claims, asa whole, encompass the disclosure of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1: FIG. 1 shows an embodiment of a polymeric precursor compound(MPP-CAIGS). As shown in FIG. 1, the structure of the compound can berepresented by the formula (RE)₂BABABB, wherein A is the repeat unit{M^(A)(ER)₂}, B is the repeat unit {M^(B)(ER)₂}, E is a chalcogen, and Ris a functional group.

FIG. 2: FIG. 2 shows an embodiment of a polymeric precursor compound(MPP-CAIGS). As shown in FIG. 2, the structure of the compound can berepresented by the formula (RE)₂BABABBABAB, wherein A is the repeat unit{M^(A)(ER)₂}, B is the repeat unit {M^(B)(ER)₂}, E is a chalcogen, and Ris a functional group.

FIG. 3: FIG. 3 shows an embodiment of a polymeric precursor compound(MPP-CAIGS). As shown in FIG. 3, the structure of the compound can berepresented by the formula (RE)₂BA(BA)_(n)BB, wherein A is the repeatunit {M^(A)(ER)₂}, B is the repeat unit {M^(B)(ER)₂}, E is a chalcogen,and R is a functional group.

FIG. 4: FIG. 4 shows an embodiment of a polymeric precursor compound(MPP-CAIGS). As shown in FIG. 4, the structure of the compound can berepresented by the formula (RE)₂BA(BA)_(n)B(BA)_(m)B, wherein A is therepeat unit {M^(A)(ER)₂}, B is the repeat unit {M^(B)(ER)₂}, E is achalcogen, and R is a functional group.

FIG. 5: FIG. 5 shows an embodiment of a polymeric precursor compound(MPP-CAIGS). As shown in FIG. 5, the structure of the compound can berepresented by the formula ^(cyclic)(BA)₄, wherein A is the repeat unit{M^(A)(ER)₂}, B is the repeat unit {M^(B)(ER)₂}, E is a chalcogen, and Ris a functional group.

FIG. 6: Schematic representation of embodiments of this invention inwhich polymeric precursors and ink compositions are deposited ontoparticular substrates by methods including spraying, coating, andprinting, and are used to make semiconductor and optoelectronicmaterials and devices, as well as energy conversion systems.

FIG. 7: Schematic representation of a solar cell embodiment of thisinvention.

FIG. 8: FIG. 8 shows the transition of a polymeric precursor embodiment(MPP) of this invention represented by the repeat unit formula{Cu_(0.7)Ag_(0.25)(Se^(s)Bu)_(3.95)In_(0.3)Ga_(0.4)Al_(0.3)} into aCu_(0.7)Ag_(0.25)In_(0.3)Ga_(0.4)Al_(0.3)Se₂ material as determined bythermogravimetric analysis.

FIG. 9: FIG. 9 shows the transition of a polymeric precursor embodiment(MPP) of this invention represented by the repeat unit formula{Cu_(0.5)Ag_(0.5)(Se^(s)Bu)₄In_(0.7)Al_(0.3)} into aCu_(0.5)Ag_(0.5)In_(0.7)Al_(0.3)Se₂ material as determined bythermogravimetric analysis.

FIG. 10: FIG. 10 shows the transition of a polymeric precursorembodiment (MPP) of this invention represented by the repeat unitformula {Ag_(0.50)Cu_(0.50)(Se^(s)Bu)_(4.0)Al_(0.30)In_(0.70)} into aAg_(0.50)Cu_(0.50)Al_(0.30)In_(0.70)Se₂ material as determined bythermogravimetric analysis.

FIG. 11: FIG. 11 shows the transition of a polymeric precursorembodiment (MPP) of this invention represented by the repeat unitformula {Cu_(0.9)(Se^(s)Bu)_(3.90)Al_(0.25)In_(0.5)Ga_(0.25)} into aCu_(0.9)Al_(0.25)In_(0.5)Ga_(0.25)Se₂ material as determined bythermogravimetric analysis.

FIG. 12: FIG. 12 shows the transition of a polymeric precursorembodiment (MPP) of this invention represented by the repeat unitformula {Cu(Se^(s)Bu)₄Al} into a CuAlSe₂ material as determined bythermogravimetric analysis.

FIG. 13: FIG. 13 shows the transition of a polymeric precursorembodiment (MPP) of this invention represented by the repeat unitformula {Cu_(0.9)(Se^(s)Bu)_(3.9)Ga_(0.7)Al_(0.3)} into aCu_(0.9)Ga_(0.7)Al_(0.3)Se₂ material as determined by thermogravimetricanalysis.

FIG. 14: FIG. 14 shows the transition of a polymeric precursorembodiment (MPP) of this invention represented by the repeat unitformula {Cu_(0.9)(Se^(s)Bu)_(3.9)In_(0.8)Al_(0.2)} into aCu_(0.9)In_(0.8)Al_(0.2)Se₂ material as determined by thermogravimetricanalysis.

FIG. 15: FIG. 15 shows the transition of a polymeric precursorembodiment (MPP) of this invention represented by the repeat unitformula {Ag(Se^(s)Bu)₄Al} into a AgAlSe₂ material as determined bythermogravimetric analysis.

FIG. 16: FIG. 16 shows the transition of a polymeric precursorembodiment (MPP) of this invention represented by the repeat unitformula {Ag(Se^(s)Bu)₄In_(0.7)Al_(0.3)} into a AgIn_(0.7)Al_(0.3)Se₂material as determined by thermogravimetric analysis.

FIG. 17: FIG. 17 shows results of methods for stoichiometric control ofthe composition of a polymeric precursor embodiment (MPP) of thisinvention. The x-axis refers to the weight percent of a particular atom,either Al, In or Ga, in the monomer compounds used to prepare thepolymeric precursor. The y-axis refers to the weight percent of aparticular atom in the precursor compound as synthesized. The straightline correlation observed in FIG. 17 shows that the stoichiometry of thepolymeric precursor can be precisely controlled with the quantities ofthe monomers used to make the polymeric precursors.

DETAILED DESCRIPTION

This disclosure provides a range of novel polymeric compounds,compositions, materials and methods for semiconductor and optoelectronicmaterials and devices including thin film photovoltaics and varioussemiconductor band gap materials.

Among other advantages, the polymeric compounds, compositions, materialsand methods of this invention can provide a precursor compound formaking semiconductor and optoelectronic materials, including CAIGASabsorber layers for solar cells and other devices. In some embodiments,the optoelectronic source precursor compounds of this invention can beused alone, without other compounds, to prepare a layer from whichCAIGAS and other materials can be made. CAIGAS refers to(Cu,Ag)(In,Ga,Al)(S,Se), and includes AIGAS, CIGAS and further materialsdescribed below.

Polymeric precursor compounds may also be used in a mixture withadditional compounds to control stoichiometry of a layer or material.

In general, the ability to select a predetermined stoichiometry inadvance means that the stoichiometry is controllable.

This invention provides polymeric compounds and compositions forphotovoltaic applications, as well as devices and systems for energyconversion, including solar cells.

The polymeric compounds and compositions of this disclosure includepolymeric precursor compounds and polymeric precursors for materials forpreparing novel semiconductor and photovoltaic materials, films, andproducts. Among other advantages, this disclosure provides stablepolymeric precursor compounds for making and using layered materials andphotovoltaics, such as for solar cells and other uses.

A photovoltaic absorber material of this disclosure can retain theprecise stoichiometry of the precursor used to make the absorbermaterial.

Polymeric precursors can advantageously form a thin, uniform film. Insome embodiments, a polymeric precursor is an oil that can be processedand deposited in a uniform layer on a substrate. This invention providespolymeric precursors that can be used neat to make a thin film, or canbe processed in an ink composition for deposition on a substrate. Thepolymeric precursors of this invention can have superior processabilityto form a thin film for making photovoltaic absorber layers and solarcells.

In certain aspects, this invention provides polymeric precursorcompounds having enhanced solubility in organic solvents. The solubilityof a polymeric precursor makes it advantageous for preparingphotovoltaic materials using any one of various processes that requiredeposition of the precursor on a substrate, such as for making thin filmsolar cells. A polymeric precursor may have enhanced solubility in oneor more carriers for preparing an ink to be deposited on a substrate.

In further embodiments, this invention provides a range of polymericprecursor compounds for which the solubility can advantageously becontrolled and selectively varied. In these embodiments, the solubilityof a polymeric precursor can be enhanced by variation of the nature andmolecular size and weight of one or more organic ligands attached to thecompound. The control of polymeric precursor solubility can allow thepreparation of inks having controlled viscosity, for example, amongother properties.

In general, the structure and properties of the polymeric compounds,compositions, and materials of this invention provide advantages inmaking photovoltaic layers, semiconductors, and devices regardless ofthe morphology, architecture, or manner of fabrication of thesemiconductors or devices.

The polymeric precursor compounds of this invention are desirable forpreparing semiconductor materials and compositions. A polymericprecursor may have a chain structure containing two or more differentmetal atoms which may be bound to each other through interactions orbridges with one or more chalcogen atoms of chalcogen-containingmoieties.

With this structure, when a polymeric precursor is used in a processsuch as deposition, coating or printing on a substrate or surface, aswell as processes involving annealing, sintering, thermal pyrolysis, andother semiconductor manufacturing processes, use of the polymericprecursors can enhance the formation of a semiconductor and itsproperties.

The polymeric precursor compounds and compositions of this invention mayadvantageously be used in processes for solar cells that avoidadditional sulfurization or selenization steps.

For example, the use of a polymeric precursor in semiconductormanufacturing processes can enhance the formation of M-E-M′ bonding,such as is required for chalcogen-containing semiconductor compounds andmaterials, wherein M is an atom of one of Groups 3 to 12, M′ is an atomof Group 13, and E is a chalcogen.

In some embodiments, a polymeric precursor compound may contain achalcogenide bridge having the formula M^(A)(E)M^(A), MB(E)M^(B) orM^(A)(E)M^(B).

A polymeric precursor compound may advantageously contain linkagesbetween atoms, where the linkages are desirably found in a material ofinterest, such as a CAIGAS, CIGAS or AIGAS material, which can be madefrom the polymeric precursor, or a combination of polymeric precursors.

The polymeric precursor compounds of this disclosure are stable andadvantageously allow control of the stoichiometry, structure, and ratiosof the atoms in a semiconductor material or layer, in particular, themetal atoms.

Using polymeric precursor compounds in any particular semiconductormanufacturing process, the stoichiometry of the metal atoms can bedetermined and controlled. The structure of a polymeric precursor maycontain a number of different metal atoms. Polymeric precursors havingdifferent metal atoms, and different numbers of metal atoms can becontacted in precise amounts to control the metal atom stoichiometry ina semiconductor manufacturing process. For processes operating atrelatively low temperatures, such as certain printing, spraying, anddeposition methods, the polymeric precursor compounds can maintain thedesired stoichiometry. As compared to processes involving multiplesources for semiconductor preparation, the polymeric precursors of thisinvention can provide enhanced control of the uniformity and propertiesof a semiconductor material.

These advantageous features allow enhanced control over the structure ofa semiconductor material made with the polymeric precursor compounds ofthis invention. The polymeric precursors of this disclosure can besuperior building blocks for semiconductor materials.

The polymeric precursor compounds, compositions and methods of thisdisclosure may allow direct and precise control of the stoichiometricratios of metal atoms. For example, in some embodiments, a polymericprecursor can be used alone, without other compounds, to readily preparea layer from which CAIGAS, CIGAS or AIGAS materials of any arbitrarystoichiometry can be made.

In certain aspects, polymeric precursor compounds can be used to formnanoparticles that can be used in various methods to preparesemiconductor materials. Embodiments of this invention may furtherprovide processes using nanoparticles made from polymeric precursors toenhance the formation and properties of a semiconductor material.

In aspects of this invention, chemically and physically uniformsemiconductor layers can be prepared with polymeric precursor compounds.The compounds and compositions of this disclosure are useful to preparesemiconductor layers having enhanced properties.

In further embodiments, solar cells and other products can be made inprocesses operating at relatively low temperatures using the polymericprecursor compounds and compositions of this disclosure.

The polymeric precursors of this disclosure are useful to prepare inksthat can be used in various methods to prepare semiconductor materials.For processes involving inks of polymeric precursors, this disclosurecan provide enhanced processability for solar cell production.

Certain polymeric precursor compounds and compositions of thisdisclosure provide the ability to be processed at relatively lowtemperatures, as well as the ability to use a variety of substratesincluding flexible polymers in solar cells.

Embodiments of Polymeric Precursors for CAIGAS Absorbers for Solar Cells

Embodiments of this invention include:

A compound comprising repeating units {M^(B)(ER)(ER)} and{M^(A)(ER)(ER)}, wherein each M^(A) is Cu or Ag, each M^(B) is In, Ga orAl, each E is S, Se, or Te, and R is independently selected, for eachoccurrence, from alkyl, aryl, heteroaryl, alkenyl, amido, silyl, andinorganic and organic ligands. Each E can be sulfur or selenium. Acompound may be a CAIGAS, AIGAS or CIGAS precursor compound.

A compound comprising two or more repeating units {M^(B)(ER)(ER)} andtwo or more repeating units {M^(A)(ER)(ER)}, wherein each M^(A) is Cu orAg, each M^(B) is In, Ga or Al, each E is S, Se, or Te, and R isindependently selected, for each occurrence, from alkyl, aryl,heteroaryl, alkenyl, amido, silyl, and inorganic and organic ligands.

A compound comprising repeating units {M^(B)(ER)(ER)} or{M^(A)(ER)(ER)}, wherein each M^(A) is Cu or Ag, each M^(B) is In, Ga orAl, each E is S, Se, or Te, and R is independently selected, for eachoccurrence, from alkyl, aryl, heteroaryl, alkenyl, amido, silyl, andinorganic and organic ligands.

A polymeric compound comprising repeating units {M^(B)(ER)(ER)} and{M^(B)(ER)(ER)}, wherein each M^(A) is Cu or Ag, each M^(B) is In, Ga orAl, each E is S, Se, or Te, and R is independently selected, for eachoccurrence, from alkyl, aryl, heteroaryl, alkenyl, amido, silyl, andinorganic and organic ligands.

A compound may have the empirical formula(Cu_(1−x)Ag_(x))_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)((S_(1−z)Se_(z))R)_(w),wherein x is from 0 to 1, y is from 0 to 1, t is from 0 to 1, the sum ofy plus t is from 0 to 1, z is from 0 to 1, u is from 0.5 to 1.5, v isfrom 0.5 to 1.5, w is from 2 to 6, and R represents R groups, of whichthere are w in number, which are independently selected from alkyl,aryl, heteroaryl, alkenyl, amido, silyl, and inorganic and organicligands. A compound above wherein x is from 0 to 0.5, y is from 0 to 1,t is from 0 to 1, the sum of y plus t is from 0 to 1, z is from 0 to 1,u is from 0.7 to 1.1, v is from 0.9 to 1.2, and w is from 2 to 6. Acompound above wherein x is from 0 to 0.3, y is from 0 to 1, t is from 0to 1, the sum of y plus t is from 0 to 1, z is from 0 to 1, u is from0.7 to 1.1, v is 1, and w is from 3 to 5. A compound above wherein x isfrom 0 to 0.2, y is from 0 to 1, t is from 0 to 1, the sum of y plus tis from 0 to 1, z is from 0 to 1, u is from 0.7 to 1.1, v is 1, and w isfrom 3.5 to 4.5.

A compound may be an inorganic polymer or coordination polymer. Acompound may be linear, branched, cyclic, or a mixture of any of theforegoing. Each R may be independently selected, for each occurrence,from (C1-8)alkyl. A compound may be an oil at a temperature below about100° C. A compound may have three or more repeating units{M^(B)(ER)(ER)}. A compound may have three or more repeating units{M^(A)(ER)(ER)}.

A compound can have the formula (AB)_(n), wherein A is the repeat unit{M^(A)(ER)(ER)}, B is the repeat unit {M^(B)(ER)(ER)}, n is one or more,or n is two or more, or n is three or more, and R is independentlyselected, for each occurrence, from alkyl, aryl, heteroaryl, alkenyl,amido, silyl, and inorganic and organic ligands. A compound can be analternating copolymer, a block copolymer, or a random copolymer.

A compound can have any one of the formulas: (RE)₂-BB(AB)_(n),(RE)₂-B(AB)_(n)B, (RE)₂-B(AB)_(n)B(AB)_(m), (RE)₂-(BA)_(n)BB,(RE)₂-B(BA)_(n)B, (RE)₂-(BA)_(n)B(BA)_(m)B, ^(cyclic)(AB)_(n),^(cyclic)(BA)_(n), (RE)₂-(BB)(AABB)_(n), (RE)₂-(BB)(AABB)_(n)(AB)_(m),(RE)₂-(B)(AABB)_(n)(B)(AB)_(m), (RE)₂-[B(AB)_(n]) ⁻, (RE)₂-[(BA)_(n)B]⁻,

(RE)₂-BB(AB¹)_(n)(AB²)_(m), (RE)₂-BB(AB¹)_(n)(AB²)_(m)(AB¹)_(p),(RE)₂-BB(AB¹)_(n)(AB²)_(m)(AB¹)_(p), (RE)₂-BB(A¹B)_(n)(A²B)_(m),(RE)₂-BB(A¹B)_(n)(A²B)_(m)(A¹B)_(p), and a mixture of any of theforegoing, wherein A is the repeat unit {M^(A)(ER)(ER)}, B is the repeatunit {M^(B)(ER)(ER)}, p is one or more, n is one or more, or n is two ormore, or n is three or more, and m is one or more.

A compound may have any one of the repeat unit formulas:{Cu_(0.7)Ag_(0.25)(Se^(s)Bu)_(3.95)In_(0.3)Ga_(0.4)Al_(0.3)},{Ga_(0.5)Al_(0.5)(Se^(s)Bu)_(3.9)Cu_(0.5)Ag_(0.4)},{Cu_(0.5)Ag_(0.5)(Se^(s)Bu)₄In_(0.7)Al_(0.3)},{Cu_(0.9)In_(0.5)Ga_(0.25)Al_(0.25)(Se^(s)Bu)_(3.9)},{Cu_(0.5)(Se^(s)Bu)₄Al}, {Cu_(0.9)(Se^(s)Bu)_(3.9)Ga_(0.7)Ag_(0.3)},{Cu_(0.9)(Se^(s)Bu)_(3.9)In_(0.8)Al_(0.2)}, {Ag(Se^(s)Bu)₄Al},{Ag(Se^(s)Bu)₄In_(0.7)Al_(0.3)},{Cu_(0.5)Ag_(0.5)(Se^(s)Bu)₄(In,Ga,Al)},{Cu_(0.7)Ag_(0.1)(Se^(s)Bu)_(3.8)Ga_(0.2)In_(0.7)Al_(0.1)},{Cu_(0.8)Ag_(0.2)(Se^(s)Bu)₄(In,Ga,Al)},{Cu_(0.2)Ag_(0.8)(Se^(s)Bu)₄(In,Ga,Al)},{Cu_(0.5)Ag_(0.5)(Se^(s)Bu)₄Ga_(0.45)In_(0.8)Al_(0.05)},{Cu_(0.85)Ag_(0.1)(Se^(s)Bu)_(3.95)Ga_(0.15)In_(0.7)Al_(0.15)},{Cu_(0.5)Ag_(0.5)(Se^(s)Bu)₄Ga_(0.3)In_(0.7)Al_(0.01)},{Cu_(0.8)Ag_(0.05)(Se^(s)Bu)_(3.85)Ga_(0.3)In_(0.3)Al_(0.4)},{(Cu,Ag)(Se^(t)Bu)(Se^(n)Bu)(In,Ga,Al)(Se^(n)Bu)₂},{(Cu,Ag)(S^(t)Bu)(S^(i)Pr)(In,Ga,Al)(S^(i)Pr)₂},{Cu_(1.40)Ag_(0.10)(Se^(t)Bu)_(1.5)(Se^(n)Bu)(In_(0.7)Ga_(0.25)Al_(0.05))(Se^(n)Bu)₂};{Cu_(1.30)Ag_(0.10)(S^(t)Bu)_(1.4)(S^(t)Bu)(In_(0.85)Ga_(0.1)Al_(0.05))(S^(t)Bu)₂};{Cu_(1.20)Ag_(0.10)(S^(t)Bu)_(1.3)(S^(n)Bu)(In_(0.80)Ga_(0.15)Al_(0.05))(S^(n)Bu)₂};{Cu_(1.10)Ag_(0.10)(Se^(t)Bu)_(1.2)(Se^(n)Bu)(In_(0.75)Ga_(0.20)Al_(0.05))(Se^(n)Bu)₂};{Cu_(1.05)Ag_(0.05)(S^(t)Bu)_(1.1)(Se^(t)Bu)(In_(0.7)Ga_(0.2)Al_(0.1))(Se^(t)Bu)₂};{Cu_(0.90)Ag_(0.10)(S^(t)Bu)(Se^(n)Bu)(In_(0.7)Ga_(0.25)Al_(0.05))(Se^(n)Bu)₂};{Cu_(0.85)Ag_(0.10)(S^(t)Bu)_(0.95)(S^(t)Bu)(In_(0.85)Ga_(0.1)Al_(0.05))(S^(t)Bu)₂};{Cu_(0.80)Ag_(0.20)(S^(t)Bu)(S^(n)Bu)(In_(0.80)Ga_(0.15)Al_(0.05))(S^(n)Bu)₂};{Cu_(0.75)Ag_(0.20)(Se^(t)Bu)_(0.95)(Se^(n)Bu)(In_(0.75)Ga_(0.20)Al_(0.05))(Se^(n)Bu)₂};{Cu_(0.70)Ag_(0.30)(S^(t)Bu)(Se^(t)Bu)(In_(0.7)Ga_(0.2)Al_(0.1))(S^(t)Bu)₂};{Cu_(0.65)Ag_(0.30)(Se^(t)Bu)_(0.95)(S^(t)Bu)(In_(0.6)Ga_(0.3)Al_(0.1))(S^(t)Bu)₂};{Cu_(0.60)Ag_(0.40)(Se^(t)Bu)₂(In_(0.5)Ga_(0.4)Al_(0.1))(Se^(t)Bu)₂};{Cu_(0.50)Ag_(0.50)(Se^(t)Bu)(Se^(n)Bu)(In_(0.5)Ga_(0.4)Al_(0.1))(Se^(n)Bu)₂};{Cu_(0.30)Ag_(0.65)(S^(t)Bu)_(0.95)(S^(t)Bu)(In_(0.5)Ga_(0.5)Al_(0.1))(S^(t)Bu)₂};{Cu_(0.30)Ag_(0.70)(S^(t)Bu)(S^(n)Bu)(In_(0.4)Ga_(0.5)Al_(0.1))(Se^(n)Bu)₂};{Cu_(0.20)Ag_(0.75)(Se^(t)Bu)_(0.95)(Se^(n)Bu)(In_(0.4)Ga_(0.5)Al_(0.1))(S^(n)Bu)₂};{Cu_(0.20)Ag_(0.80)(S^(t)Bu)(Se^(t)Bu)(In_(0.3)Ga_(0.1)Al_(0.6))(Se^(t)Bu)₂};{Cu_(0.10)Ag_(0.85)(Se^(t)Bu)_(0.95)(S^(t)Bu)(In_(0.3)Ga_(0.6)Al_(0.1))(S^(t)Bu)₂};and{Cu_(0.10)Ag_(0.90)(Se^(t)Bu)₂(In_(0.2)Ga_(0.7)Al_(0.1))(Se^(t)Bu)₂}.

An ink comprising one or more compounds above and one or more carriers.An ink may be a solution of the compounds in an organic carrier. An inkmay contain a dopant or alkali dopant. An ink may contain one or morecomponents selected from the group of a surfactant, a dispersant, anemulsifier, an anti-foaming agent, a dryer, a filler, a resin binder, athickener, a viscosity modifier, an anti-oxidant, a flow agent, aplasticizer, a conductivity agent, a crystallization promoter, anextender, a film conditioner, an adhesion promoter, and a dye. An inkcan contain one or more components selected from the group of aconducting polymer, silver metal, silver selenide, silver sulfide,copper metal, indium metal, gallium metal, zinc metal, an alkali metal,an alkali metal salt, an alkaline earth metal salt, a sodiumchalcogenate, a calcium chalcogenate, cadmium sulfide, cadmium selenide,cadmium telluride, indium sulfide, indium selenide, indium telluride,gallium sulfide, gallium selenide, gallium telluride, zinc sulfide, zincselenide, zinc telluride, copper sulfide, copper selenide, coppertelluride, molybdenum sulfide, molybdenum selenide, molybdenumtelluride, and mixtures of any of the foregoing.

A method for making a precursor compound comprising:

a) providing monomer compounds M^(B1)(ER)³, M^(B2)(ER)₃, M^(B3)(ER)³,M^(A1)(ER) and M^(A2)(ER); and

b) contacting the monomer compounds;

wherein M^(B1) is In, M^(B2) is Ga, M^(B3) is Al, M^(A1) is Cu, andM^(A2) is Ag, each E is S, Se, or Te, and each R is independentlyselected, for each occurrence, from alkyl, aryl, heteroaryl, alkenyl,amido, silyl, and inorganic and organic ligands. M^(A1) and M^(A2) mayboth be Cu, or M^(A1) and M^(A2) can both be Ag. Each E is sulfur orselenium. The compound may be a CAIGAS, AIGAS or CIGAS precursorcompound. The compound can be deficient in a Group 11 atom. The monomercompounds may be contacted in a process of depositing, spraying,coating, or printing. The monomer compounds can be contacted at atemperature of from about −60° C. to about 100° C., or from about 0° C.to about 200° C.

A compound made by a process comprising reacting monomers M^(B1)(ER)₃,M^(B2)(ER)₃, M^(B3)(ER)₃, M^(A1)(ER) and M^(A2)(ER), wherein M^(B1) isIn, M^(B2) is Ga, M^(B3) is Al, M^(A1) is Cu, and M^(A2) is Ag, each Eis S, Se, or Te, and R is independently selected, for each occurrence,from alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganic andorganic ligands. The compound above wherein M^(A1) and M^(A2) are bothCu, or M^(A1) and M^(A2) are both Ag. The compound above wherein each Eis sulfur or selenium. The compound above wherein the compound is aCAIGAS, AIGAS or CIGAS precursor compound. The compound above whereinthe compound has the empirical formula(Cu_(1−x)Ag_(x))_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)((S_(1−z)Se_(z))R)_(w),wherein x is from 0 to 1, y is from 0 to 1, t is from 0 to 1, the sum ofy plus t is from 0 to 1, z is from 0 to 1, u is from 0.5 to 1.5, v isfrom 0.5 to 1.5, w is from 2 to 6, and R represents R groups, of whichthere are w in number, which are independently selected from alkyl,aryl, heteroaryl, alkenyl, amido, silyl, and inorganic and organicligands. The compound above wherein x is from 0 to 0.5, y is from 0 to1, t is from 0 to 1, the sum of y plus t is from 0 to 1, z is from 0 to1, u is from 0.7 to 1.1, v is from 0.9 to 1.2, and w is from 2 to 6. Thecompound above wherein x is from 0 to 0.3, y is from 0 to 1, t is from 0to 1, the sum of y plus t is from 0 to 1, z is from 0 to 1, u is from0.7 to 1.1, v is 1, and w is from 3 to 5. The compound above wherein xis from 0 to 0.2, y is from 0 to 1, t is from 0 to 1, the sum of y plust is from 0 to 1, z is from 0 to 1, u is from 0.7 to 1.1, v is 1, and wis from 3.5 to 4.5.

An article comprising one or more compounds or inks described abovedeposited onto a substrate. The article above wherein the depositing isdone by spraying, spray coating, spray deposition, spray pyrolysis,printing, screen printing, inkjet printing, aerosol jet printing, inkprinting, jet printing, stamp/pad printing, transfer printing, padprinting, flexographic printing, gravure printing, contact printing,reverse printing, thermal printing, lithography, electrophotographicprinting, electrodepositing, electroplating, electroless plating, bathdeposition, coating, wet coating, spin coating, knife coating, rollercoating, rod coating, slot die coating, meyerbar coating, lip directcoating, capillary coating, liquid deposition, solution deposition,layer-by-layer deposition, spin casting, solution casting, andcombinations of any of the forgoing. The article above wherein thesubstrate is selected from the group of a semiconductor, a dopedsemiconductor, silicon, gallium arsenide, insulators, glass, molybdenumglass, silicon dioxide, titanium dioxide, zinc oxide, silicon nitride, ametal, a metal foil, molybdenum, aluminum, beryllium, cadmium, cerium,chromium, cobalt, copper, gallium, gold, lead, manganese, molybdenum,nickel, palladium, platinum, rhenium, rhodium, silver, stainless steel,steel, iron, strontium, tin, titanium, tungsten, zinc, zirconium, ametal alloy, a metal silicide, a metal carbide, a polymer, a plastic, aconductive polymer, a copolymer, a polymer blend, a polyethyleneterephthalate, a polycarbonate, a polyester, a polyester film, a mylar,a polyvinyl fluoride, polyvinylidene fluoride, a polyethylene, apolyetherimide, a polyethersulfone, a polyetherketone, a polyimide, apolyvinylchloride, an acrylonitrile butadiene styrene polymer, asilicone, an epoxy, paper, coated paper, and combinations of any of theforgoing. The article above wherein the substrate is a shaped substrateincluding a tube, a cylinder, a roller, a rod, a pin, a shaft, a plane,a plate, a blade, a vane, a curved surface or a spheroid.

A method for making an article, the method comprising:

(a) providing one or more compounds or inks described above;

(b) providing a substrate; and

(c) depositing the compounds or inks onto the substrate.

The method above wherein step (c) is repeated. The method above furthercomprising heating the substrate at a temperature of from about 100° C.to about 400° C. to convert the compounds or inks to a material. Themethod above further comprising heating the substrate at a temperatureof from about 100° C. to about 400° C. to convert the compounds or inksto a material, followed by repeating step (c). The method above furthercomprising annealing the material by heating the substrate at atemperature of from about 300° C. to about 650° C. The method abovefurther comprising heating the substrate at a temperature of from about100° C. to about 400° C. to convert the compounds or inks to a material,and annealing the material by heating the substrate at a temperature offrom about 300° C. to about 650° C. The method above further comprisingheating the substrate at a temperature of from about 100° C. to about400° C. to convert the compounds or inks to a material, depositing thecompounds or inks onto the substrate, and annealing the material byheating the substrate at a temperature of from about 300° C. to about650° C.

The method above further comprising:

(d) heating the substrate at a temperature of from about 100° C. toabout 400° C. to convert the compounds or inks to a material;

(e) depositing the compounds or inks onto the substrate;

(f) repeating steps (d) and (e); and

(g) annealing the material by heating the substrate at a temperature offrom about 300° C. to about 650° C.

The method above further comprising:

(d) heating the substrate at a temperature of from about 100° C. toabout 400° C. to convert the compounds or inks to a material;

(e) annealing the semiconductor material by heating the substrate at atemperature of from about 300° C. to about 650° C.; and

(f) repeating steps (c), (d) and (e).

The method above further comprising an optional step of selenization orsulfurization, either before, during or after any step of heating orannealing.

A material having the empirical formula(Cu_(1−x)Ag_(x))_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)(S_(1−z)Se_(z))_(w),where x is from 0 to 1, y is from 0 to 1, t is from 0.001 to 1, the sumof y plus t is from 0.001 to 1, z is from 0 to 1, u is from 0.5 to 1.5,v is from 0.5 to 1.5, and w is from 1 to 3. The material above wherein xis from 0 to 0.5, y is from 0 to 1, t is from 0.001 to 0.5, z is from0.5 to 1, u is from 0.7 to 1.1, v is from 0.9 to 1.1, and w is from 1.8to 2.4. The material above wherein x is from 0 to 0.3, y is from 0 to 1,t is from 0.001 to 0.3, z is from 0.5 to 1, u is from 0.7 to 1.1, v is1, and w is from 1.8 to 2.4. The material above wherein x is from 0 to0.2, y is from 0 to 1, t is from 0.001 to 0.2, z is from 0.5 to 1, u isfrom 0.7 to 1.1, v is 1, and w is from 2.0 to 2.4. The material abovewherein the material is a semiconductor. The material above wherein thematerial is in the form of a thin film. An optoelectronic devicecomprising the material above.

A method for making a material comprising,

(a) providing one or more compounds or inks above;

(b) providing a substrate;

(c) depositing the compounds or inks onto the substrate; and

(d) heating the substrate at a temperature of from about 20° C. to about650° C. in an inert atmosphere, thereby producing a material having athickness of from 0.001 to 100 micrometers. The method above wherein thesubstrate is heated at a temperature of from about 100° C. to about 550°C., or from about 200° C. to about 400° C. A photovoltaic devicecomprising a material made by the method above.

A thin film material made by a process comprising,

(a) providing one or more compounds or inks above;

(b) providing a substrate;

(c) depositing the compounds or inks onto the substrate; and

(d) heating the substrate at a temperature of from about 20° C. to about650° C. in an inert atmosphere, thereby producing a thin film materialhaving a thickness of from 0.001 to 100 micrometers. The thin filmmaterial above wherein the substrate is heating at a temperature of fromabout 100° C. to about 550° C., or from about 200° C. to about 400° C.The thin film material above, the process further comprising an optionalstep of selenization or sulfurization, either before, during or aftersteps (c) or (d). A photovoltaic absorber made with a thin film materialabove. A photovoltaic device comprising a thin film material above.

A photovoltaic absorber having the empirical formula(Cu_(1−x)Ag_(x))_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)(S_(1−z)Se_(z))_(w),where x is from 0 to 1, y is from 0 to 1, t is from 0.001 to 1, the sumof y plus t is from 0.001 to 1, z is from 0 to 1, u is from 0.5 to 1.5,v is from 0.5 to 1.5, and w is from 1 to 3. The photovoltaic absorberabove wherein x is from 0 to 0.5, y is from 0 to 1, t is from 0.001 to0.5, z is from 0.5 to 1, u is from 0.7 to 1.1, v is from 0.9 to 1.1, andw is from 1.8 to 2.4. The photovoltaic absorber above wherein x is from0 to 0.3, y is from 0 to 1, t is from 0.001 to 0.3, z is from 0.7 to 1,u is from 0.7 to 1.1, v is 1, and w is from 1.8 to 2.4. The photovoltaicabsorber above wherein x is from 0 to 0.2, y is from 0 to 1, t is from0.001 to 0.2, z is from 0.8 to 1, u is from 0.7 to 1.1, v is 1, and w isfrom 2.0 to 2.4. A photovoltaic device comprising the photovoltaicabsorber above. A system for providing electrical power comprising aphotovoltaic device above. A method for providing electrical powercomprising using a photovoltaic system above to convert light intoelectrical energy.

A method for making a photovoltaic absorber layer on a substratecomprising,

(a) providing one or more compounds or inks above;

(b) providing a substrate;

(c) depositing the compounds or inks onto the substrate; and

(d) heating the substrate at a temperature of from about 100° C. toabout 650° C. in an inert atmosphere, thereby producing a photovoltaicabsorber layer having a thickness of from 0.001 to 100 micrometers. Themethod above wherein the substrate is heating at a temperature of fromabout 100° C. to about 550° C., or from about 200° C. to about 400° C.The method above further comprising an optional step of selenization orsulfurization, either before, during or after steps (c) or (d). Aphotovoltaic device comprising a photovoltaic absorber layer made by themethod above.

Empirical Formulas of Precursor Compounds

This disclosure provides a range of polymeric precursor compounds havingtwo or more different metal atoms and chalcogen atoms.

In certain aspects, a polymeric precursor compound contains metal atoms,and atoms of Group 13, as well as combinations thereof. Any of theseatoms may be bonded to one or more atoms selected from atoms of Group15, S, Se, and Te, as well as one or more ligands.

A polymeric precursor compound may be a neutral compound, or an ionicform, or have a charged complex or counterion. In some embodiments, anionic form of a polymeric precursor compound may contain a divalentmetal atom, or a divalent metal atom as a counterion.

A polymeric precursor compound may contain atoms selected from thetransition metals of Group 3 through Group 12, B, Al, Ga, In, Tl, Si,Ge, Sn, Pb, As, Sb, and Bi. Any of these atoms may be bonded to one ormore atoms selected from atoms of Group 15, S, Se, and Te, as well asone or more ligands.

A polymeric precursor compound may contain atoms selected from Ni, Pd,Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, and Bi.Any of these atoms may be bonded to one or more atoms selected fromatoms of Group 15, S, Se, and Te, as well as one or more ligands.

In some embodiments, a polymeric precursor compound may contain atomsselected from Cu, Ag, Zn, Ga, In, Al, Tl, Si, Ge, Sn, and Pb. Any ofthese atoms may be bonded to one or more atoms selected from atoms ofGroup 15, S, Se, and Te, as well as one or more ligands.

In some embodiments, a polymeric precursor compound may contain atomsselected from Cu, Ag, Zn, Ga, In, Al, Tl, Si, Ge, Sn, and Pb. Any ofthese atoms may be bonded to one or more chalcogen atoms, as well as oneor more ligands.

In some variations, a polymeric precursor compound may contain atomsselected from Cu, Ag, In, Ga and Al. Any of these atoms may be bonded toone or more atoms selected from S, Se, and Te, as well as one or moreligands.

Polymeric Precursor Structure and Properties (MPP-CAIGAS)

A polymeric precursor compound of this disclosure can be stable atambient temperatures. Polymeric precursors can be used for makinglayered materials, optoelectronic materials, and devices. Usingpolymeric precursors advantageously allows control of the stoichiometry,structure, and ratios of various atoms in a material, layer, orsemiconductor.

Polymeric precursor compounds of this invention may be solids, solidswith low melting temperatures, semisolids, flowable solids, gums, orrubber-like solids, oily substances, or liquids at ambient temperatures,or temperatures moderately elevated from ambient. Embodiments of thisdisclosure that are fluids at temperatures moderately elevated fromambient can provide superior processability for production of solarcells and other products, as well as the enhanced ability to beprocessed on a variety of substrates including flexible substrates.

In general, a polymeric precursor compound can be processed through theapplication of heat, light, kinetic, mechanical or other energy to beconverted to a material, including a semiconductor material. In theseprocesses, a polymeric precursor compound undergoes a transition tobecome a material. The conversion of a polymeric precursor compound to amaterial can be done in processes known in the art, as well as the novelprocesses of this disclosure.

Embodiments of this invention may further provide processes for makingoptoelectronic materials. Following the synthesis of a polymericprecursor compound, the compound can be deposited, sprayed, or printedonto a substrate by various means. Conversion of the polymeric precursorcompound to a material can be done during or after the process ofdepositing, spraying, or printing the compound onto the substrate.

A polymeric precursor compound of this disclosure may have a transitiontemperature below about 400° C., or below about 300° C., or below about280° C., or below about 260° C., or below about 240° C., or below about220° C., or below about 200° C.

In some aspects, polymeric precursors of this disclosure includemolecules that are melt processable at temperatures below about 100° C.In certain aspects, a polymeric precursor can be fluid, flowable,flowable melt, or semisolid at relatively low temperatures and can beprocessed as a neat solid, semisolid, neat flowable melt, flowablesolid, gum, rubber-like solid, oily substance, or liquid. In certainembodiments, a polymeric precursor is melt processable as a flowablemelt at a temperature below about 200° C., or below about 180° C., orbelow about 160° C., or below about 140° C., or below about 120° C., orbelow about 100° C., or below about 80° C., or below about 60° C., orbelow about 40° C.

A polymeric precursor compound of this invention can be crystalline oramorphous, and can be soluble in various non-aqueous solvents.

A polymeric precursor compound may contain ligands, or ligand fragments,or portions of ligands that can be removed under mild conditions, atrelatively low temperatures, and therefore provide a facile route toconvert the polymeric precursor to a material or semiconductor. Theligands, or some atoms of the ligands, may be removable in variousprocesses, including certain methods for depositing, spraying, andprinting, as well as by application of energy.

These advantageous features allow enhanced control over the structure ofa semiconductor material made with the polymeric precursor compounds ofthis invention.

Polymeric Precursors for Semiconductors and Optoelectronics (MPP-CAIGAS)

This invention provides a range of polymeric precursor structures,compositions, and molecules having two or more different metal atoms.

In some embodiments, a polymeric precursor compound contains atoms M^(B)of Group 13 selected from Ga, In, Al, and a combination thereof.

The atoms M^(B) may be any combination of atoms of Ga, In and Al.

These polymeric precursor compounds further contain monovalent metalatoms M^(A) selected from Cu, Ag, and a mixture thereof.

The atoms M^(A) may be any combination of atoms of Cu and Ag.

The polymeric precursors of this disclosure can be considered inorganicpolymers or coordination polymers.

The polymeric precursors of this disclosure may be represented indifferent ways, using different formulas to describe the same structure.

In some aspects, a polymeric precursor of this disclosure may be adistribution of polymer molecules or chains. The distribution mayencompass molecules or chains having a range of chain lengths ormolecular sizes. A polymeric precursor can be a mixture of polymers,polymer molecules or chains. The distribution of a polymeric precursorcan be centered or weighted about a particular molecular weight or chainmass.

Embodiments of this invention further provide polymeric precursors thatcan be described as AB alternating addition copolymers.

The AB alternating addition copolymer is in general composed of repeatunits A and B. The repeat units A and B are each derived from a monomer.The repeat units A and B may also be referred to as being monomers,although the empirical formula of monomer A is different from theempirical formula of repeat unit A.

The monomer for M^(A) can be M^(A)(ER), where M^(A) is Cu or Ag.

The monomer for M^(B) can be M^(B)(ER)₃, where M^(B) is Ga, In, Al, orany mixture of Ga, In and Al.

In a polymeric precursor, monomers of A link to monomers of B to providea polymer chain, whether linear, cyclic, or branched, or of any othershape, that has repeat units A, each having the formula {M^(A)(ER)₂},and repeat units B, each having the formula {M^(B)(ER)₂}. The repeatunits A and B may appear in alternating order in the chain, for example,•••ABABABABAB•••.

In some embodiments, a polymeric precursor may have atoms M^(B) of Ga,In and Al where the different atoms appear in random order in thestructure.

The polymeric precursor compounds of this invention may be made with anydesired stoichiometry with respect to the number of different Group 13elements and their respective ratios. The stoichiometry of a polymericprecursor compound may be controlled through the concentrations ofmonomers, or repeating units in the polymer chains of the precursors. Apolymeric precursor compound may be made with any desired stoichiometrywith respect to the number of different Group 13 elements and theirrespective ratios.

In some aspects, this disclosure provides polymeric precursors which areinorganic AB alternating addition copolymers having one of the followingFormulas 1 through 13:

(RE)₂-[B(AB)_(n)]⁻  Formula 1

(RE)₂-[(BA)_(n)B]⁻  Formula 2

(RE)₂-BB(AB)_(n)  Formula 3

(RE)₂-B(AB)_(n)B  Formula 4

(RE)₂-B(AB)_(n)B(AB)_(m)  Formula 5

(RE)₂-(BA)_(n)BB  Formula 6

(RE)₂-B(BA)_(n)B  Formula 7

(RE)₂-(BA)_(n)B(BA)_(m)B  Formula 8

^(cyclic)(AB)_(n)  Formula 9

^(cyclic)(BA)_(n)  Formula 10

(RE)₂-(BB)(AABB)_(n)  Formula 11

(RE)₂-(BB)(AABB)_(n)(AB)_(m)  Formula 12

(RE)₂-(B)(AABB)_(n)(B)(AB)_(m)  Formula 13

where A and B are as defined above, E is S, Se, or Te, and R is definedbelow.

Formulas 1 and 2 describe ionic forms that have a counterion orcounterions not shown. Examples of counterions include alkali metalions, Na, Li, and K.

The formulas RE-B(AB)_(n) and RE-(BA)_(n)B may describe stable moleculesunder certain conditions.

For example, an embodiment of a polymeric precursor compound of Formula4 is shown in FIG. 1. As shown in FIG. 1, the structure of the compoundcan be represented by the formula (RE)₂BABABB, wherein A is the repeatunit {M^(A)(ER)₂}, B is the repeat unit {M^(B)(ER)₂}, E is a chalcogen,and R is a functional group defined below.

In another example, an embodiment of a polymeric precursor compound ofFormula 5 is shown in FIG. 2. As shown in FIG. 2, the structure of thecompound can be represented by the formula (RE)₂BABABBABAB, wherein A isthe repeat unit {M^(A)(ER)₂}, B is the repeat unit {M^(B)(ER)₂}, E is achalcogen, and R is a functional group defined below.

In a further example, an embodiment of a polymeric precursor compound ofFormula 6 is shown in FIG. 3. As shown in FIG. 3, the structure of thecompound can be represented by the formula (RE)₂BA(BA)_(n)BB, wherein Ais the repeat unit {M^(A)(ER)₂}, B is the repeat unit {M^(B)(ER)₂}, E isa chalcogen, and R is a functional group defined below.

In another example, an embodiment of a polymeric precursor compound ofFormula 8 is shown in FIG. 4. As shown in FIG. 4, the structure of thecompound can be represented by the formula (RE)₂BA(BA)_(n)B(BA)_(m)B,wherein A is the repeat unit {M^(A)(ER)₂}, B is the repeat unit{M^(B)(ER)₂}, E is a chalcogen, and R is a functional group definedbelow.

In a further example, an embodiment of a polymeric precursor compound ofFormula 10 is shown in FIG. 5. As shown in FIG. 5, the structure of thecompound can be represented by the formula ^(cyclic)(BA)₄, wherein A isthe repeat unit {M^(A)(ER)₂}, B is the repeat unit {M^(B)(ER)₂}, E is achalcogen, and R is a functional group defined below.

A polymeric precursor having one of Formulas 1-8 and 11-13 may be of anylength or molecular size. The values of n and m can be one (1) or more.In certain embodiments, the values of n and m are 2 or more, or 3 ormore, or 4 or more, or 5 or more, or 6 or more, or 7 or more, or 8 ormore, or 9 or more, or 10 or more. In some embodiments, n and m areindependently from 2 to about one million, or from 2 to about 100,000,or from 2 to about 10,000, or from 2 to about 5000, or from 2 to about1000, or from 2 to about 500, or from 2 to about 100, or from 2 to about50.

A cyclic polymeric precursor having one of Formulas 9 or 10 may be ofany molecular size. The value of n may be two (2) or more. In certainvariations, the values of n and m are 2 or more, or 3 or more, or 4 ormore, or 5 or more, or 6 or more, or 7 or more, or 8 or more, or 9 ormore, or 10 or more. In some embodiments, for cyclic Formulas 9 and 10,n is from 2 to about 50, or from 2 to about 20, or from 2 to about 16,or from 2 to about 14, or from 2 to about 12, or from 2 to about 10, orfrom 2 to about 8.

In another aspect, the repeat units {M^(B)(ER)₂} and {M^(A)(ER)₂} may beconsidered “handed” because the metal atom M^(A) and the Group 13 atomM^(B) appear on the left, while the chalcogen atom E appears to theright side. Thus, a linear terminated chain will in general require anadditional chalcogen group or groups on the left terminus, as inFormulas 1-8 and 11-13, to complete the structure. A cyclic chain, asdescribed by Formulas 9 and 10, does not require an additional chalcogengroup or groups for termination.

In certain aspects, structures of Formulas 1-8 and 11-13, where n and mare one (1), may be described as adducts. For example, adducts include(RE)₂-BBAB, (RE)₂-BABB, and (RE)₂-BABBAB.

In some embodiments, a polymeric precursor may include a structure thatis an AABB alternating block copolymer. For example, a polymericprecursor or portions of a precursor structure may contain one or moreconsecutive repeat units {AABB}. A polymeric precursor having an AABBalternating block copolymer may be represented by Formula 11 above.

In some aspects, this disclosure provides polymeric precursors which areinorganic AB alternating addition copolymers having the repeat units ofFormula 14

where atoms M^(B) are atoms of Group 13 selected from Ga and In, and Eis S, Se, or Te.

In certain aspects, this invention provides polymeric precursors havinga number n of the repeat units of Formula 14, where n may be 1 or more,or 2 or more, or 3 or more, or 4 or more, or 5 or more, or 6 or more, or7 or more, or 8 or more, or 9 or more, or 10 or more, or 11 or more, or12 or more.

The AB copolymer of Formula 14 may also be represented as (AB)_(n) or(BA)_(n), which represents a polymer of any chain length. Another way torepresent certain AB copolymers is the formula •••ABAB•••.

In further variations, this invention provides polymeric precursors thatmay be represented by Formula 15

where atoms M^(B1) and M^(B2) are the same or different atoms of Group13 selected from Ga, In and Al, E is S, Se, or Te, and p is one (1) ormore.

In further aspects, this invention provides polymeric precursors whichmay be represented by Formula 16

where atoms M^(B1) and M^(B2) are the same or different atoms of Group13 selected from Ga In and Al, atoms M^(A1) and M^(A2) are the same ordifferent and are atoms selected from Cu and Ag, E is S, Se, or Te, andp is one (1) or more.

In another aspect, this disclosure provides inorganic AB alternatingcopolymers which may be represented by Formula 17

••••••AB¹AB²AB³••••••  Formula 17

where B¹, B², and B³ are repeat units containing atoms M^(B1), M^(B2),and M^(B3), respectively, which are atoms of Ga and In.

Certain examples of empirical formulas for monomers and polymericprecursors of this invention are summarized in Table 1.

TABLE 1 Empirical formulas for monomers, repeat units and polymericprecursors Formula Representative Constitutional Chain Unit DescriptionA {M^(A)(ER)₂} From monomer M^(A)(ER), where M^(A) is Cu or Ag B{M^(B)(ER)₂} From monomer M^(B)(ER)₃ , where M^(B) is Ga, In, Al AB{M^(A)(ER)₂M^(B)(ER)₂} Polymer chain repeat unit ABA{M^(A)(ER)₂M^(B)(ER)₂M^(A)(ER)₂} An adduct, trimer, or oligomer B¹AB²{M^(B1)(ER)₂M^(A)(ER)₂M^(B2)(ER)₂} Polymer chain repeat unit, M^(B1) andM^(B2) may be the same or different, a trimer or oligomer AB¹AB²{M^(A)(ER)₂M^(B1)(ER)₂M^(A)(ER)₂M^(B2)(ER)₂} Alternating copolymer(AB)_(n), a tetramer or oligomer AB¹AB²AB³{M^(A)(ER)₂M^(B1)(ER)₂M^(A)(ER)₂M^(B2)(ER)₂M^(A)(ER)₂M^(B1)(ER)₂}Polymer, or an AB trimer, or an oligomer (AB)_(n) or (BA)_(n)

Polymer of any chain length •••ABAB••• A—B—A—B Polymer of any length,whether linear, branched, or cyclic {AABB} A—A—B—B AABB alternatingblock copolymer ^(cyclic)(AB)₄ or ^(cyclic)(BA)₄

Cyclic polymer chain, oligomer or octamer

In Table 1, the “representative constitutional chain unit” refers to therepeating unit of the polymer chain. In general, the number andappearance of electrons, ligands, or R groups in a representativeconstitutional chain repeating unit does not necessarily reflect theoxidation state of the metal atom. For example, the chain repeating unitA, which is {M^(A)(ER)₂}, arises from the monomer M^(A)(ER), where M^(A)is a metal atom of monovalent oxidation state 1 (I or one) selected fromCu and Ag. It is to be understood that the repeating unit exists in thepolymer chain bonded to two other repeating units, or to a repeatingunit and a chain terminating unit. Likewise, the chain repeating unit B,which is {M^(B)(ER)₂}, arises from the monomer M^(B)(ER)₃, where M^(B)is a Group 13 atom of trivalent oxidation state 3 (III or three)selected from Ga, In, Al, and a mixture thereof. In one aspect, monomerM^(A)(ER), and monomer M^(B)(ER)₃, combine to form an AB repeating unit,which is {M^(A)(ER)₂M^(B)(ER)₂}.

In some aspects, this disclosure provides AB alternating copolymerswhich may also be alternating with respect to M^(A) or M^(B). Apolymeric precursor that is alternating with respect to M^(A) maycontain chain regions having alternating atoms M^(A1) and M^(A2). Apolymeric precursor that is alternating with respect to M^(B) maycontain chain regions having alternating atoms M^(B1) and M^(B2).

In further aspects, this disclosure provides AB alternating blockcopolymers which may contain one or more blocks of n repeat units,represented as (AB¹)_(n) or (B¹A)_(n), where the block of repeat unitscontains only one kind of atom M^(B1) selected from Group 13. A blockmay also be a repeat unit represented as (A¹B)_(n) or (BA¹)_(n), wherethe block of repeat units contains only one kind of atom M^(A1). Apolymeric precursor of this disclosure may contain one or more blocks ofrepeat units having different Group 13 atoms in each block, or differentatoms M^(A) in each block. For example, a polymeric precursor may haveone of the following formulas:

(RE)₂-BB(AB¹)_(n)(AB²)_(m)  Formula 18

(RE)₂-BB(AB¹)_(n)(AB²)_(m)(AB¹)_(p)  Formula 19

(RE)₂-BB(AB¹)_(n)(AB²)_(m)(AB¹)_(p)  Formula 20

(RE)₂-BB(A¹B)_(n)(A²B)_(m)  Formula 21

(RE)₂-BB(A¹B)_(n)(A²B)_(m)(A¹B)_(p)  Formula 22

where B¹, B² represent repeat units {M^(B1)(ER)₂} and {M^(B2)(ER)₂},respectively, where M^(B1), M^(B2) are In, Ga, respectively, and whereA¹, A² represent repeat units {M^(A1)(ER)₂} and {M^(A2)(ER)₂},respectively, where M^(A1), M^(A2) are Cu and Ag, respectively. InFormulas 18 through 22, the values of n, m, and p may be 2 or more, or 3or more, or 4 or more, or 5 or more, or 6 or more, or 7 or more, or 8 ormore, or 9 or more, or 10 or more, or 11 or more, or 12 or more.

In certain embodiments, an M^(B) monomer can contain a chelating group-ERE-, for example, having the formula M^(B)(ERE).

In some embodiments, a monomer may exist in a dimeric form under ambientconditions, or a trimeric or higher form, and can be used as a reagentin such forms. It is understood that the term monomer would refer to allsuch forms, whether found under ambient conditions, or found during theprocess for synthesizing a polymeric precursor from the monomer. Theformulas M^(A)(ER) and M^(B)(ER)₃, for example, should be taken toencompass the monomer in such naturally-occurring dimeric or higherforms, if any. A monomer in a dimeric or higher form, when used as areagent can provide the monomer form. For example, compounds of theempirical formula Cu(ER) may occur in aggregated forms that areinsoluble, and when used as a reagent can provide the monomer form forreaction with M^(B)(ER)₃.

The polymeric precursors of this invention, which can be obtained byreacting, for example, monomers M^(A)(ER) and M^(B)(ER)₃, can beadvantageously highly soluble in organic solvents. The monomersthemselves may have been less soluble, or insoluble. Thus, in someaspects, the polymeric precursors of this invention may advantageouslybe used in processes for making photovoltaic layers and other articleswhich involve deposition of compounds using organic solvents.

As used herein, the terms “polymer” and “polymeric” refer to apolymerized moiety, a polymerized monomer, a repeating chain made ofrepeating units, or a polymer chain or polymer molecule. A polymer orpolymer chain may be defined by recitation of its repeating unit orunits, and may have various shapes or connectivities such as linear,branched, cyclic, and dendrimeric. Unless otherwise specified, the termspolymer and polymeric include homopolymers, copolymers, blockcopolymers, alternating polymers, terpolymers, polymers containing anynumber of different monomers, oligomers, networks, two-dimensionalnetworks, three-dimensional networks, crosslinked polymers, short andlong chains, high and low molecular weight polymer chains,macromolecules, and other forms of repeating structures such asdendrimers. Polymers include those having linear, branched and cyclicpolymer chains, and polymers having long or short branches.

As used herein, the term “polymeric component” refers to a component ofa composition, where the component is a polymer, or may form a polymerby polymerization. The term polymeric component includes a polymerizablemonomer or polymerizable molecule. A polymeric component may have anycombination of the monomers or polymers which make up any of the examplepolymers described herein, or may be a blend of polymers.

Embodiments of this invention may further provide polymeric precursorshaving polymer chain structures with repeating units. The stoichiometryof these polymeric precursors may be precisely controlled to provideaccurate levels of any desired arbitrary ratio of particular atoms.Precursor compounds having controlled stoichiometry can be used to makebulk materials, layers, and semiconductor materials having controlledstoichiometry. In some aspects, precisely controlling the stoichiometryof a polymeric precursor may be achieved by controlling thestoichiometry of the reagents, reactants, monomers or compounds used toprepare the polymeric precursor.

For the polymeric precursors of this invention, the group R in theformulas above, or a portion thereof, may be a good leaving group inrelation to a transition of the polymeric precursor compound at elevatedtemperatures or upon application of energy.

The functional groups R in the formulas above and in Table 1 may each bethe same or different from the other and are groups attached through acarbon or non-carbon atom, including alkyl, aryl, heteroaryl, alkenyl,amido, silyl, and inorganic and organic ligands. In some embodiments,the groups R are each the same or different from the other and are alkylgroups attached through a carbon atom.

In some aspects, the monomer for M^(B) can be represented asM^(B)(ER¹)₃, and the monomer for M^(A) can be represented as M^(A)(ER²),where R¹ and R² are the same or different and are groups attachedthrough a carbon or non-carbon atom, including alkyl, aryl, heteroaryl,alkenyl, amido, silyl, and inorganic and organic ligands. In someembodiments, the groups R¹ and R² are each the same or different fromthe other and are alkyl groups attached through a carbon atom.

In certain variations, the monomer for M^(B) may be M^(B)(ER¹)(ER²)₂,where R¹ and R² are different and are groups attached through a carbonor non-carbon atom, including alkyl, aryl, heteroaryl, alkenyl, amido,silyl, and inorganic and organic ligands. In some embodiments, thegroups R¹ and R², of M^(B)(ER¹)(ER²)₂, are different and are alkylgroups attached through a carbon atom.

In some embodiments, polymeric precursor compounds advantageously do notcontain a phosphine ligand, or a ligand or attached compound containingphosphorus, arsenic, or antimony, or a halogen ligand.

In further embodiments, the groups R may independently be (C1-22)alkylgroups. In these embodiments, the alkyl group may be a (C1)alkyl(methyl), or a (C2)alkyl (ethyl), or a (C3)alkyl, or a (C4)alkyl, or a(C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a (C8)alkyl, or a(C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a (C12)alkyl, or a(C13)alkyl, or a (C14)alkyl, or a (C15)alkyl, or a (C16)alkyl, or a(C17)alkyl, or a (C18)alkyl, or a (C19)alkyl, or a (C20)alkyl, or a(C21)alkyl, or a (C22)alkyl.

In certain embodiments, the groups R may independently be (C1-12)alkylgroups. In these embodiments, the alkyl group may be a (C1)alkyl(methyl), or a (C2)alkyl (ethyl), or a (C3)alkyl, or a (C4)alkyl, or a(C5)alkyl, or a (C6)alkyl, or a (C7)alkyl, or a (C8)alkyl, or a(C9)alkyl, or a (C10)alkyl, or a (C11)alkyl, or a (C12)alkyl.

In certain embodiments, the groups R may independently be (C16)alkylgroups. In these embodiments, the alkyl group may be a (C1)alkyl(methyl), or a (C2)alkyl (ethyl), or a (C3)alkyl, or a (C4)alkyl, or a(C5)alkyl, or a (C6)alkyl.

A polymeric precursor compound may be crystalline, or non-crystalline.

In some embodiments, a polymeric precursor may be a compound comprisingrepeating units {M^(B)(ER)(ER)} and {M^(A)(ER)(ER)}, wherein M^(A) is amonovalent metal atom selected from Cu and Ag, M^(B) is an atom of Group13, E is S, Se, or Te, and R is independently selected, for eachoccurrence, from alkyl, aryl, heteroaryl, alkenyl, amido, silyl, andinorganic and organic ligands. In certain embodiments, the atoms M^(B)in the repeating units {M^(B)(ER)(ER)} are randomly selected from atomsof Group 13. In certain variations, M^(A) is (Cu,Ag) and the atoms M^(B)are selected from indium, gallium and aluminum. E may be only seleniumin a polymeric precursor, and the groups R may be independentlyselected, for each occurrence, from (C1-6)alkyl.

Embodiments of this invention may further provide polymeric precursorsthat are linear, branched, cyclic, or a mixture of any of the foregoing.Some polymeric precursors may be a flowable melt at a temperature belowabout 100° C.

In some aspects, a polymeric precursor may contain n repeating units{M^(B)(ER)(ER)} and n repeating units {M^(A)(ER)(ER)}, wherein n is oneor more, or n is two or more, or n is four or more, or n is eight ormore. The repeating units {M^(B)(ER)(ER)} and {M^(A)(ER)(ER)} may bealternating. A polymeric precursor may be described by the formula(AB)_(n), wherein A is the repeat unit {M^(B)(ER)(ER)}, B is the repeatunit {M^(B)(ER)(ER)}, n is one or more, or n is two or more, and R isindependently selected, for each occurrence, from alkyl, aryl,heteroaryl, alkenyl, amido, silyl, and inorganic and organic ligands. Insome variations, a polymeric precursor may have any one of the formulas(RE)₂-BB(AB)_(n), (RE)₂-B(AB)_(n)B, (RE)₂-B(AB)_(n)B(AB)_(m),(RE)₂-(BA)_(n)BB, (RE)₂-B(BA)_(n)B, (RE)₂-(BA)_(n)B(BA)_(m)B,^(cyclic)(AB)_(n), ^(cyclic)(BA)_(n), (RE)₂-(BB)(AABB)_(n),(RE)₂-(BB)(AABB)_(n)(AB)_(m), (RE)₂-(B)(AABB)_(n)(B)(AB)_(m),(RE)₂-[B(AB)_(n)]⁻, and (RE)₂-[(BA)_(n)B]⁻, wherein A is the repeat unit{M^(A)(ER)(ER)}, B is the repeat unit {M^(B)(ER)(ER)}, n is one or more,or n is two or more, and m is one or more. In further aspects, apolymeric precursor may be a block copolymer containing one or moreblocks of repeat units, wherein each block contains only one kind ofatom M^(B).

A precursor compound of this disclosure may be a combination of u*(1−x)equivalents of M^(A1)(ER), u*x equivalents of M^(A2)(ER), v*(1−y−t)equivalents of M^(B1)(ER)₃, v*y equivalents of M^(B2)(ER)₃, v*tequivalents of M^(B3)(ER)₃, wherein M^(A1) is Cu and M^(A2) is Ag,M^(B1), M^(B2) and M^(B3) are different atoms of Group 13, wherein thecompound has the empirical formula (M^(A1) _(1−x)M^(A2) _(x))_(u)(M^(B1)_(1−y−t)M^(B2) _(y)M^(B3) _(t))_(v)((S_(1−z)Se_(z))R)_(w), wherein x isfrom 0 to 1, y is from 0 to 1, t is from 0 to 1, the sum of y plus t isfrom 0 to 1, z is from 0 to 1, u is from 0.5 to 1.5, v is from 0.5 to1.5, w is from 2 to 6, and R represents R groups, of which there are win number, and are independently selected from alkyl, aryl, heteroaryl,alkenyl, amido, silyl, and inorganic and organic ligands. In theseembodiments, a precursor compound can have the stoichiometry useful toprepare CAIGAS, CIGAS and AIGAS materials, including materials deficientor enriched in the quantity of a Group 11 atom. In certain embodiments,M^(B2) is In, and y is 0.65 to 0.85.

In further embodiments, a precursor compound can contain S, Se and Te.

A precursor compound of this disclosure may contain a quantity of atomsof Group 11 from 0.33 to 3, or from 0.33 to 1, or from 1 to 2, or from 2to 3, as a ratio of moles of atoms of Group 11 to the total moles ofatoms of Group 13, for example as the ratio (Cu plus Ag) to (In plus Gaplus Al), or (Cu⁺ Ag):(In +Ga⁺ Al).

In some embodiments, a precursor compound can be a combination ofw*(1−z) equivalents of M^(A1)(ER¹), w*z equivalents of M^(A2)(ER²), xequivalents of M^(B1)(ER³)₃, y equivalents of M^(B2)(ER⁴)₃, tequivalents of M^(B3)(ER⁵)₃, wherein M^(A1) is Cu and M^(A2) is Ag,M^(B1), M^(B2) and M^(B3) are different atoms of Group 13, wherein thecompound has the empirical formula(Cu_(1−z)Ag_(z))_(w)In_(x)Ga_(y)Al_(t)(ER¹)_(w(1−z))(ER²)_((w*z))(ER³)_(3x)(ER⁴)_(3y)(ER⁵)_(3t),w is from 0.5 to 1.5, z is from 0 to 1, x is from 0 to 1, y is from 0 to1, t is from 0 to 1, x plus y plus t is one, and wherein R¹, R², R³, R⁴and R⁵ are the same or each different, and are independently selected,for each occurrence, from alkyl, aryl, heteroaryl, alkenyl, amido,silyl, and inorganic and organic ligands. In these embodiments, aprecursor compound can have the stoichiometry useful to prepare CAIGAS,CIGAS and AIGAS materials, including materials deficient or enriched inthe quantity of a Group 11 atom.

A precursor compound of this disclosure may be a combination of xequivalents of M^(A1)(ER), v*(1−y−t) equivalents of M^(B1)(ER)₃, v*yequivalents of M^(B2)(ER)₃, v*t equivalents of M^(B3)(ER)₃, whereinM^(A1) is Cu, M^(B1), M^(B2) and M^(B3) are different atoms of Group 13,wherein the compound has the empirical formula M^(A1) _(x)(M^(B1)_(1−y−t)M^(B2) _(y)M^(B3) _(t))_(v)((S_(1−z)Se_(z))R)_(w), wherein x isfrom 0.5 to 1.5, y is from 0 to 1, t is from 0 to 1, the sum of y plus tis from 0 to 1, z is from 0 to 1, v is from 0.5 to 1.5, w is from 2 to6, and R represents R groups, of which there are w in number, and areindependently selected from alkyl, aryl, heteroaryl, alkenyl, amido,silyl, and inorganic and organic ligands. In these embodiments, aprecursor compound can have the stoichiometry useful to prepare CIGASmaterials, including materials deficient or enriched in the quantity ofa Group 11 atom.

In some embodiments, a precursor compound can be a combination of zequivalents of M^(A1)(ER¹), x equivalents of M^(B1)(ER³)³, y equivalentsof M^(B2)(ER⁴)₃, t equivalents of M^(B3)(ER⁵)₃, wherein M^(A1) is Cu,M^(B1), M^(B2) and M^(B3) are different atoms of Group 13, wherein thecompound has the empirical formulaCu_(z)In_(x)Ga_(y)Al_(t)(ER¹)_(w(1−z))(ER²)_((w*z))(ER³)_(3x)(ER⁴)_(3y)(ER⁵)_(3t),z is from 0.5 to 1.5, x is from 0 to 1, y is from 0 to 1, t is from 0 to1, x plus y plus t is one, and wherein R¹, R², R³, R⁴ and R⁵ are thesame or each different, and are independently selected, for eachoccurrence, from alkyl, aryl, heteroaryl, alkenyl, amido, silyl, andinorganic and organic ligands. In these embodiments, a precursorcompound can have the stoichiometry useful to prepare CIGAS and CIGSmaterials, including materials deficient or enriched in the quantity ofa Group 11 atom.

A polymeric precursor molecule can be represented by the formula{M^(A)(ER)(ER)M^(B)(ER)(ER)}, or {M^(A)(ER)₂M^(B)(ER)₂}, which are eachunderstood to represent an {AB} repeating unit of a polymeric precursor(AB)_(n). This shorthand representation is used in the followingparagraphs to describe further examples of polymeric precursors.Further, when more than one kind of atom M^(B) is present, the amount ofeach kind may be specified in these examples by the notation (x M^(B1),yM^(B2)). For example, the polymeric compound {Ag(Se^(n)Bu)₂(0.75 In,0.25 Ga)(Se^(n)Bu)₂}, which can also be written{Ag(Se^(n)Bu)₄In_(0.75)Ga_(0.25)}, is composed of repeating units, wherethe repeating units appear in random order, and 75% of the repeatingunits contain an indium atom and 25% contain a gallium atom.

Examples of polymeric precursor compounds of this disclosure includecompounds having any one of the repeat unit formulas:{Cu_(0.7)Ag_(0.25)(Se^(s)Bu)_(3.95)In_(0.3)Ga_(0.4)Al_(0.3)},{Cu_(0.5)Ag_(0.5)(Se^(s)Bu)₄In_(0.7)Al_(0.3)}, {Cu(Se^(s)Bu)₄Al},{Cu_(0.9)(Se^(s)Bu)_(3.9)Ga_(0.7)Al_(0.3)},{Cu_(0.9)(Se^(s)Bu)_(3.9)In_(0.8)Al_(0.2)}, {Ag(Se^(s)Bu)₄Al},{Ag(Se^(s)Bu)₄In_(0.7)Al_(0.3)}.

Examples of an MPP-CAIGAS polymeric precursor compounds of thisdisclosure include compounds having any one of the repeat unit formulas:{Cu_(0.7)Ag_(0.25)(Se^(s)Bu)_(3.95)In_(0.3)Ga_(0.4)Al_(0.3)} and{Cu_(0.5)Ag_(0.5)(Se^(s)Bu)₄In_(0.7)Al_(0.3)}.

Examples of an MPP-CIGAS polymeric precursor compounds of thisdisclosure include compounds having any one of the repeat unit formulas:{Cu(Se^(s)Bu)₄Al}, {Cu_(0.9)(Se^(s)Bu)_(3.9)Ga_(0.7)Al_(0.3)}, and{Cu_(0.9)(Se^(s)Bu)_(3.9)In_(0.8)Al_(0.2)}.

Examples of an MPP-AIGAS polymeric precursor compounds of thisdisclosure include compounds having any one of the repeat unit formulas:{Ag(Se^(s)Bu)₄Al} and {Ag(Se^(s)Bu)₄In_(0.7)Al_(0.3)}.

Examples of polymeric precursor compounds of this disclosure includecompounds having any one of the repeat unit formulas:{Cu_(0.5)Ag_(0.5)(Se^(s)Bu)₄(In,Ga,Al)},{Cu_(0.7)Ag_(0.1)(Se^(s)Bu)_(3.8)Ga_(0.2)In_(0.7)Al_(0.1)},{Cu_(0.8)Ag_(0.2)(Se^(s)Bu)₄(In,Ga,Al)},{Cu_(0.2)Ag_(0.8)(Se^(s)Bu)₄(In₅Ga₅Al)},{Cu_(0.5)Ag_(0.5)(Se^(s)Bu)₄Ga_(0.45)In_(0.5)Al_(0.05)},{Cu_(0.85)Ag_(0.1)(Se^(s)Bu)_(3.95)Ga_(0.15)In_(0.7)Al_(0.15)},{Cu_(0.5)Ag_(0.5)(Se^(s)Bu)₄Ga_(0.3)In_(0.7)Al_(0.01)}, and{Cu_(0.8)Ag_(0.05)(Se^(s)Bu)_(3.85)Ga_(0.3)In_(0.3)Al_(0.4)}.

Examples of polymeric precursor compounds of this disclosure includecompounds having any one of the repeat unit formulas:{(Cu,Ag)(Se^(t)Bu)(Se^(n)Bu)(In,Ga,Al)(Se^(n)Bu)₂} and{(Cu,Ag)(S^(t)Bu)(S^(i)Pr)(In,Ga,Al)(S^(i)Pr)₂}.

Examples of polymeric precursor compounds of this disclosure includecompounds having any one of the repeat unit formulas:{Cu_(1.40)Ag_(0.10)(Se^(t)Bu)_(1.5)(Se^(n)Bu)(In_(0.7)Ga_(0.25)Al_(0.05))(Se^(n)Bu)₂};{Cu_(1.30)Ag_(0.10)(S^(t)Bu)_(1.4)(S^(t)Bu)(In_(0.85)Ga_(0.1)Al_(0.05))(S^(t)Bu)₂};{Cu_(1.20)Ag_(0.10)(S^(t)Bu)_(1.3)(S^(n)Bu)(In_(0.80)Ga_(0.15)Al_(0.05))(S^(n)Bu)₂};{Cu_(1.10)Ag_(0.10)(Se^(t)Bu)_(1.2)(Se^(n)Bu)(In_(0.75)Ga_(0.20)Al_(0.05))(Se^(n)Bu)₂};and{Cu_(1.05)Ag_(0.05)(S^(t)Bu)_(1.1)(Se^(t)Bu)(In_(0.7)Ga_(0.2)Al_(0.1))(Se^(t)Bu)₂}.

Example of polymeric precursor compounds of this disclosure includecompounds having any one of the repeat unit formulas:{Cu_(0.90)Ag_(0.10)(Se^(t)Bu)(Se^(n)Bu)(In_(0.7)Ga_(0.25)Al_(0.05))(Se^(n)Bu)₂};{Cu_(0.85)Ag_(0.10)(S^(t)Bu)_(0.95)(S^(t)Bu)(In_(0.85)Ga_(0.1)Al_(0.05))(S^(t)Bu)₂};{Cu_(0.80)Ag_(0.20)(S^(t)Bu)(S^(n)Bu)(In_(0.80)Ga_(0.15)Al_(0.05))(S^(n)Bu)₂};{Cu_(0.75)Ag_(0.20)(Se^(t)Bu)_(0.95)(Se^(n)Bu)(In_(0.75)Ga_(0.20)Al_(0.05))(Se^(n)Bu)₂};{Cu_(0.70)Ag_(0.30)(S^(t)Bu)(Se^(t)Bu)(In_(0.7)Ga_(0.2)Al_(0.1))(Se^(t)Bu)₂};{Cu_(0.65)Ag_(0.30)(Se^(t)Bu)_(0.05)(S^(t)Bu)(In_(0.6)Ga_(0.3)Al_(0.1))(S^(t)Bu)₂};{Cu_(0.60)Ag_(0.40)(Se^(t)Bu)₂(In_(0.5)Ga_(0.4)Al_(0.1))(Se^(t)Bu)₂};{Cu_(0.50)Ag_(0.50)(Se^(t)Bu)(Se^(n)Bu)(In_(0.5)Ga_(0.4)Al_(0.1))(Se^(n)Bu)₂};{Cu_(0.30)Ag_(0.65)(S^(t)Bu)_(0.95)(S^(t)Bu)(In_(0.5)Ga_(0.4)Al_(0.1))(S^(t)Bu)₂};{Cu_(0.30)Ag_(0.70)(S^(t)Bu)(Se^(n)Bu)(In_(0.4)Ga_(0.5)Al_(0.1))(S^(n)Bu)₂};{Cu_(0.20)Ag_(0.75)(Se^(t)Bu)_(0.95)(Se^(n)Bu)(In_(0.4)Ga_(0.5)Al_(0.1))(Se^(n)Bu)₂};{Cu_(0.20)Ag_(0.80)(S^(t)Bu)(Se^(t)Bu)(In_(0.3)Ga_(0.1)Al_(0.6))(Se^(t)Bu)₂};{Cu_(0.10)Ag_(0.85)(Se^(t)Bu)_(0.95)(S^(t)Bu)(In_(0.3)Ga_(0.6)Al_(0.1))(S^(t)Bu)₂};and{Cu_(0.10)Ag_(0.90)(Se^(t)Bu)₂(In_(0.2)Ga_(0.7)Al_(0.1))(Se^(t)Bu)₂}.

Preparation of Polymeric Precursors (MPP-CAIGAS)

Embodiments of this invention provide a family of polymeric precursormolecules and compositions which can be synthesized from a compoundcontaining an atom M^(B) of Group 13 selected from Ga, In and Al, and acompound containing a monovalent atom M^(A) selected from Cu and Ag.

Advantageously facile routes for the synthesis and isolation ofpolymeric precursor compounds of this invention have been discovered, asdescribed below.

This disclosure provides a range of polymeric precursor compositionswhich can be transformed into semiconductor materials andsemiconductors. In some aspects the polymeric precursor compositions areprecursors for the formation of semiconductor materials andsemiconductors.

In general, the polymeric precursor compositions of this invention arenon-oxide chalcogen compositions.

In some embodiments, the polymeric precursor compositions are sources orprecursors for the formation of absorber layers for solar cells,including CAIGAS, AIGAS and CIGAS absorber layers.

A polymeric precursor compound may be made with any desiredstoichiometry with respect to the number of different Group 13 elementsand their respective ratios.

As discussed below, a polymeric precursor compound may be made byreacting monomers to produce a polymer chain. The polymeric precursorformation reactions can include initiation, propagation, andtermination.

Methods for making a polymeric precursor may include the step ofcontacting a compound M^(B)(ER)₃ with a compound M^(A)(ER), where M^(A),M^(B), E, and R are as defined above.

As shown in Reaction Scheme 1, a method for making a polymeric precursormay include the step of contacting a compound M^(B)(ER¹)₃ with acompound M^(A)(ER²), where M^(A), M^(B), and E are as defined above andthe groups R¹ and R² of the compounds may be the same or different andare as defined above.

In Reaction Scheme 1, M^(B)(ER¹)₃ and M^(A)(ER²) are monomers that formthe first adduct 1, M^(A)(ER)₂M^(B)(ER)₂. Reaction Scheme 1 representsthe initiation of a polymerization of monomers. In one aspect, ReactionScheme 1 represents the formation of the intermediate adduct AB. Ingeneral, among other steps, the polymerization reaction may form polymerchains by adding monomers to the first adduct 1, so that the firstadduct 1 may be a transient molecule that is not observed when a longerchain is ultimately produced. When additional monomers are bound toeither end of the first adduct 1, then the first adduct 1 becomes arepeating unit AB in the polymer chain.

In general, to prepare a polymeric precursor, the compounds M^(B)(ER)₃and M^(A)(ER) can be generated by various reactions.

For example, a compound M^(A)(ER) can be prepared by reacting M^(A)Xwith M⁺(ER). M⁺(ER) can be prepared by reacting E with LiR to provideLi(ER). Li(ER) can be acidified to provide HER, which can be reactedwith Na(OR) or K(OR) to provide Na(ER) and K(ER), respectively. In thesereactions, E, R and M^(A) are as defined above.

In another example, a compound M^(A)(ER) can be prepared by reactingM^(A)X with (RE)Si(CH₃)₃. The compound (RE)Si(CH₃)₃ can be made byreacting M⁺(ER) with XSi(CH₃)₃, where M⁺ is Na, Li, or K, and X ishalogen.

In another example, a compound M^(A)(ER) can be prepared by reactingM^(A) ₂O with HER. In particular, Cu(ER) can be prepared by reactingCu₂O with HER.

For example, a compound M^(B)(ER)₃ can be prepared by reacting M^(B)X₃with M⁺(ER). M⁺(ER) can be prepared as described above.

In another example, a compound M^(B)(ER)₃ can be prepared by reactingM^(B)X₃ with (RE)Si(CH₃)₃. The compound (RE)Si(CH₃)₃ can be made asdescribed above.

In another example, a compound M^(B)(ER)₃ can be prepared by reactingM^(B)R₃ with HER.

Moreover, in the preparation of a polymeric precursor, a compoundM⁺M^(B)(ER)₄ can optionally be used in place of a portion of thecompound M^(B)(ER)₃. For example, a compound M⁺M^(B)(ER)₄ can beprepared by reacting M^(B)X₃ with 4 equivalents of M⁺(ER), where M⁺ isNa, Li, or K, and X is halogen. The compound M⁺(ER) can be prepared asdescribed above.

The propagation of the polymeric precursor can be represented in part bythe formulas in Reaction Scheme 2. The formulas in Reaction Scheme 2represent only some of the reactions and additions which may occur inpropagation of the polymeric precursor.

In Reaction Scheme 2, the addition of a monomer M^(B)(ER¹)₃ orM^(A)(ER²) to the first adduct 1, may produce additional adducts 2 and3, respectively. In one aspect, Reaction Scheme 2 represents theformation of the adduct (RE)-BAB, as well as the adduct intermediateAB-M^(A)(ER). In general, the adducts 2 and 3 may be transient moietiesthat are not observed when a longer chain is ultimately produced.

The products of the initial propagation steps may continue to addmonomers in propagation. As shown in Reaction Scheme 3, adduct 2 may adda monomer M^(B)(ER¹)₃ or M^(A)(ER²).

In one aspect, Reaction Scheme 3 represents the formation of theintermediate adduct (RE)-BAB-M^(A)(ER)₄, as well as the adduct(RE)₂-BBAB 6. In general, the molecules 4, 5 and 6 may be transientmolecules that are not observed when a longer chain is ultimatelyproduced.

Other reactions and additions which may occur include the addition ofcertain propagating chains to certain other propagating chains. Forexample, as shown in Reaction Scheme 4, adduct 1 may add to adduct 2 toform a longer chain.

In one aspect, Reaction Scheme 4 represents the formation of the adduct(RE)-BABAB 7.

Any of the moieties 4, 5, 6, and 7 may be transient, and may not beobserved when a longer chain is ultimately produced.

In some variations, a propagation step may provide a stable molecule.For example, moiety 6 may be a stable molecule.

In general, AB alternating block copolymers as described in Formulas 18through 22 may be prepared by sequential addition of the correspondingmonomers M^(B1)(ER)₃ and M^(B2)(ER)₃, as well as M^(A1)(ER) andM^(A2)(ER) during polymerization or propagation.

Certain reactions or additions of the polymeric precursor propagationmay include the formation of chain branches. As shown in Reaction Scheme5, the addition of a monomer M^(A)(ER²) to the adduct molecule 2 mayproduce a branched chain 8.

The propagation of the polymeric precursor can be represented in part bythe formulas in Reaction Schemes 2, 3, 4 and 5. The formulas in ReactionSchemes 2, 3, 4 and 5 represent only some representative reactions andadditions which may occur in propagation of the polymeric precursor.

Termination of the propagating polymer chain may occur by severalmechanisms. In general, because of the valencies of the atoms M^(A) andM^(B), a completed polymer chain may terminate in a M^(B) unit, but notan M^(A) unit. In some aspects, a chain terminating unit is a •••B unit,or a (ER)₂B••• unit.

In some aspects, the propagation of the polymeric precursor chain mayterminate when either of the monomers M^(B)(ER)₃ or M^(A)(ER) becomesdepleted.

In certain aspects, as shown in Reaction Scheme 6, the propagation ofthe polymeric precursor chain may terminate when a growing chainrepresented by the formula (RE)-B••••••B reacts with another chainhaving the same terminal (RE)-B unit to form a chain having the formulaB••••••BB••••••B.

In Reaction Scheme 6, two chains have combined, where the propagation ofthe polymer chain is essentially terminated and the product chain(RE)₂B••••••BB••••••B has chain terminating units that are B units.

In further aspects, the propagation of the polymeric precursor chain mayterminate when the growing chain forms a ring. As shown in ReactionScheme 7, a propagating chain such as 5 may terminate by cyclization inwhich the polymer chain forms a ring.

A polymeric precursor compound may be a single chain, or a distributionof chains having different lengths, structures or shapes, such asbranched, networked, dendrimeric, and cyclic shapes, as well ascombinations of the forgoing. A polymeric precursor compound may be anycombination of the molecules, adducts and chains described above inReaction Schemes 1 through 7.

A polymeric precursor of this disclosure may be made by the process ofproviding a first monomer compound having the formula M^(B)(ER¹)₃,providing a second monomer compound having the formula M^(A)(ER²), andcontacting the first monomer compound with the second monomer compound.

In some embodiments, the first monomer compound may be a combination ofcompounds having the formulas M^(B1)(ER¹)₃, M^(B2)(ER²)₃ andM^(B3)(ER³)₃, wherein M^(B1), M^(B2) and M^(B3) are Ga, In, and Al,respectively, and R¹, R² and R³ are the same or different and areindependently selected from alkyl, aryl, heteroaryl, alkenyl, amido,silyl, and inorganic and organic ligands.

In certain aspects, the second monomer compound may be a combination ofcompounds having the formulas M^(A1)(ER⁴) and M^(A2)(ER⁵), whereinM^(A1) and M^(A2) are different atoms selected from Cu and Ag, and R⁴and R⁵ are defined the same as R¹, R² and R³.

In further aspects, a method for making a polymeric precursor mayinclude the synthesis of a compound containing two or more atoms ofM^(B) and contacting the compound with a compound M^(A)(ER), whereM^(A), M^(B), E and R are as defined above. For example,(ER)²M^(B1)(ER)₂M^(B2)(ER)₂ can be reacted with M^(A)(ER²), where M^(B1)and M^(B2) are the same or different atoms of Group 13.

Methods for making a polymeric precursor include embodiments in whichthe first monomer compound and the second monomer compound may becontacted in a process of depositing, spraying, coating, or printing. Incertain embodiments, the first monomer compound and the second monomercompound may be contacted at a temperature of from about −60° C. toabout 100° C., or from about 0° C. to about 200° C.

Controlled Stoichiometry of Polymeric Precursors (MPP-CAIGAS)

A polymeric precursor compound may be made with any desiredstoichiometry with respect to the number of different Group 13 elementsand their respective ratios.

In some embodiments, the stoichiometry of a polymeric precursor compoundmay be controlled through the numbers of equivalents of the monomers inthe formation reactions.

In some aspects, the monomers M^(B1)(ER)₃, M^(B2)(ER)₃ and M^(B3)(ER¹)₃can be used for polymerization. Examples of these monomers are In(ER)₃,Ga(ER¹)₃ and Al(ER²)₃, where the groups R, R¹ and R² are the same ordifferent and are groups attached through a carbon or non-carbon atom,including alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganicand organic ligands. In some embodiments, the groups R, R¹ and R² areeach the same or different from the others and are alkyl groups attachedthrough a carbon atom.

In further aspects, the monomers M^(B1)(ER)(ER¹)₂, M^(B2)(ER²)(ER³)² andM^(B3)(ER⁴)(ER⁵)₂ can be used for polymerization, where the groups R,R¹, R², R³, R⁴ and R⁵ are each the same or different from the others andare groups attached through a carbon or non-carbon atom, includingalkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganic andorganic ligands. In some embodiments, the groups R, R¹, R², R³, R⁴ andR⁵ are each the same or different from the others and are alkyl groupsattached through a carbon atom.

Embodiments of this invention may further provide that the stoichiometryof a polymeric precursor compound may be controlled to any desired levelthrough the adjustment of the amounts of each of the monomers providedin the formation reactions.

As shown in Reaction Scheme 8, a polymerization to form a polymericprecursor may be initiated with a mixture of monomers M^(A)(ER³),M^(B1)(ER¹)₃, and M^(B2)(ER²)₃ having any arbitrary ratios ofstoichiometry, where it is to be understood that M^(B1) and M^(B2) caneach be a mixture of Ga, In and Al.

In Reaction Scheme 8, a polymerization can be performed with a mixtureof monomers in any desired amounts. In certain variations, apolymerization to form a polymeric precursor may be initiated with amixture of any combination of the monomers described above, where thenumber of equivalents of each monomer is adjusted to any arbitrarylevel.

In some variations, a polymerization to form a polymeric precursor canbe done using the monomers M^(A1)(ER¹) and M^(A2)(ER²), for example,which can be contacted in any desired quantity to produce any arbitraryratio of M^(A1) to M^(A2).

In some aspects, for alternating copolymers of monomers M^(A)(ER) andM^(B)(ER)₃, the ratio of M^(A) to M^(B) in the polymeric precursor canbe controlled from a ratio as low as 1:2 in the unit BAB, for example,to a ratio of 1:1 in an alternating (AB)_(n) polymeric precursor, to aratio of 1.5:1 or higher. The ratio of M^(A) to M^(B) in the polymericprecursor may be 0.5 to 1.5, or 0.5 to 1, or 1 to 1, or 1 to 0.5, or 1.5to 0.5. As discussed above, in further embodiments, a polymericprecursor compound may be made with any desired stoichiometry withrespect to the number of different Group 13 elements and theirrespective ratios.

In certain aspects, a polymerization to form a polymeric precursor canbe done to form a polymeric precursor having any ratio of M^(A) toM^(B). As shown in Reaction Scheme 9, a polymeric precursor having thecomposition {p M^(A)(ER)/m M^(B1)(ER)₃/n M^(B2)(ER)₃} may be formedusing the mixture of monomers m M^(B1)(ER)₃+n M^(B2)(ER)₃+p M^(A)(ER),where it is to be understood that M^(B1) and M^(B2) can each be amixture of Ga, In and Al.

In certain variations, any number of monomers of M^(A)(ER) and anynumber of monomers of M^(B)(ER)₃ can be used in the formation reactions.For example, a polymeric precursor may be made with the monomersM^(A1)(ER), M^(A2)(ER), M^(B1)(ER)₃, and M^(B2)(ER¹)₃, where the numberof equivalents of each monomer is an independent and arbitrary amount.

For example, the ratios of the atoms M^(A):M^(B) in a polymericprecursor may be about 0.5:1 or greater, or about 0.6:1 or greater, orabout 0.7:1 or greater, or about 0.8:1 or greater, or about 0.9:1 orgreater, or about 0.95:1 or greater. In certain variations, the ratiosof the atoms M^(A): M^(B) in a polymeric precursor may be about 1:1 orgreater, or about 1.1:1 or greater.

In further examples, the ratios of the atoms M^(A): M^(B) in a polymericprecursor may be from about 0.5 to about 1.2, or from about 0.6 to about1.2, or from about 0.7 to about 1.1, or from about 0.8 to about 1.1, orfrom about 0.8 to about 1, or from about 0.9 to about 1. In someexamples, the ratios of the atoms M^(A): M^(B) in a polymeric precursormay be about 0.80, or about 0.82, or about 0.84, or about 0.86, or about0.88, or about 0.90, or about 0.92, or about 0.94, or about 0.96, orabout 0.98, or about 1.00, or about 1.02, or about 1.1, or about 1.2, orabout 1.3, or about 1.5. In the foregoing ratios M^(A):M^(B), the ratiorefers to the sum of all atoms of M^(A) or M^(B), respectively, whenthere are more than one kind of M^(A) or M^(B), such as M^(A1) andM^(A2) and M^(B1) and M^(B2).

As shown in Reaction Scheme 10, a polymeric precursor compound havingthe repeating unit composition {M^(A)(ER)₂(m M^(B1),n M^(B2))(ER)²} maybe formed using the mixture of monomers m M^(B1)(ER)₃+nM^(B2)(ER)₃+M^(A)(ER), where it is to be understood that M^(B1) andM^(B2) can each be a mixture of Ga, In and Al.

In Reaction Scheme 10, the sum of m and n is one.

Embodiments of this invention may further provide a polymeric precursormade from monomers of M^(A)(ER) and M^(B)(ER)₃, where the total numberof equivalents of monomers of M^(A)(ER) is less than the total number ofequivalents of monomers of M^(B)(ER)₃. In certain embodiments, apolymeric precursor may be made that is substoichiometric or deficientin atoms of M^(A) relative to atoms of M^(B).

As used herein, the expression M^(A) is deficient, or M^(A) is deficientto M^(B) refers to a composition or formula in which there are feweratoms of M^(A) than M^(B).

As used herein, the expression M^(A) is enriched, or M^(A) is enrichedrelative to M^(B) refers to a composition or formula in which there aremore atoms of M^(A) than M^(B).

As shown in Reaction Scheme 11, a polymeric precursor having theempirical formula (M^(A1) _(1−x)M^(A2) _(x))_(u)(M^(B1) _(1−y−t)M^(B2)_(y)M^(B3) _(t))_(v)((E¹ _(1−z)E² _(z))R)_(w) may be formed using themixture of monomers M^(B1)(ER)₃, M^(B2)(ER)₃ and M^(A)(ER), where it isto be understood that M^(B1) and M^(B2) can each be a mixture of Ga, Inand Al, and M^(A) can be a mixture of Cu and Ag.

A precursor compound of this disclosure may be a combination of u*(1−x)equivalents of Cu(ER), u*x equivalents of Ag(ER), v*(1−y−t) equivalentsof Ga(ER)₃, v*y equivalents of In(ER)₃, v*t equivalents of Al(ER)₃,wherein the compound has the empirical formula(Cu_(1−x)Ag_(x))_(u)(Ga_(1−y−t)In_(y)Al_(t))_(v)((S_(1−z)Se_(z))R)_(w),wherein x is from 0 to 1, y is from 0 to 1, t is from 0 to 1, the sum ofy plus t is from 0 to 1, z is from 0 to 1, u is from 0.5 to 1.5, v isfrom 0.5 to 1.5, w is from 2 to 6, and R represents R groups, of whichthere are w in number, and are independently selected from alkyl, aryl,heteroaryl, alkenyl, amido, silyl, and inorganic and organic ligands.

In some embodiments, a precursor compound may have the empirical formula(Cu_(1−x)Ag_(x))_(u)(Ga_(1−y−t)In_(y)Al_(t))_(v)((S_(1−z)Se_(z))R)_(w),wherein x is from 0 to 1, y is from 0 to 1, t is from 0.001 to 1, thesum of y plus t is from 0.001 to 1, z is from 0 to 1, u is from 0.5 to1.5, v is from 0.5 to 1.5, w is from 2 to 6, and R represents R groups,of which there are w in number, and are independently selected fromalkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganic andorganic ligands. In certain embodiments, t may be from 0.001 to 1, orfrom 0.01 to 1, or from 0.02 to 1, or from 0.03 to 1, or from 0.04 to 1,or from 0.05 to 1, or from 0.07 to 1, or from 0.1 to 1, or from 0.2 to1, or from 0.3 to 1, or from 0.4 to 1. In certain embodiments, x may befrom 0.001 to 1, or from 0.01 to 1, or from 0.02 to 1, or from 0.03 to1, or from 0.05 to 1, or from 0.07 to 1, or from 0.1 to 1, or from 0.2to 1, or from 0.3 to 1. In certain embodiments, t may be from 0.001 to 1and x may be from 0.001 to 1, or t may be from 0.01 to 1 and x may befrom 0.01 to 1, or t may be from 0.02 to 1 and x may be from 0.02 to 1,or t may be from 0.05 to 1 and x may be from 0.05 to 1, or t may be from0.1 to 1 and x may be from 0.1 to 1, or t may be from 0.2 to 1 and x maybe from 0.2 to 1.

A precursor compound of this disclosure may be a combination of u*(1−x)equivalents of Cu(ER), u*x equivalents of Ag(ER), v*(1−y−t) equivalentsof Ga(ER)₃, v*y equivalents of In(ER)₃, v*t equivalents of Al(ER)₃,wherein the compound has the empirical formula(Cu_(1−x)Ag_(x))_(u)(Ga_(1−y−t)In_(y)Al_(t))_(v)((S_(1−z)Se_(z))R)_(w),wherein x is from 0 to 1, y is from 0 to 1, t is from 0 to 1, the sum ofy plus t is from 0 to 1, z is from 0 to 1, u is from 0.7 to 1.25, v isfrom 0.7 to 1.25, w is from 2 to 6, and R represents R groups, of whichthere are w in number, and are independently selected from alkyl, aryl,heteroaryl, alkenyl, amido, silyl, and inorganic and organic ligands.

In some embodiments, a precursor compound can be a combination ofw*(1−z) equivalents of Cu(ER¹), w*z equivalents of Ag(ER²), xequivalents of Ga(ER³)₃, y equivalents of In(ER⁴)₃, t equivalents ofAl(ER⁵)₃, wherein the compound has the empirical formula(Cu_(1−z)Ag_(z))_(w)In_(x)Ga_(y)Al_(t)(ER¹)_(w(1−z))(ER²)_((w*z))(ER³)_(3x)(ER⁴)_(3y)(ER⁵)_(3t),w is from 0.5 to 1.5, z is from 0 to 1, x is from 0 to 1, y is from 0 to1, t is from 0 to 1, x plus y plus t is one, and wherein R¹, R², R³, R⁴and R⁵ are defined the same as above.

In some embodiments, a precursor compound can be a combination ofw*(1−z) equivalents of Cu(ER¹), w*z equivalents of Ag(ER²), xequivalents of Ga(ER³)₃, y equivalents of In(ER⁴)₃, t equivalents ofAl(ER⁵)₃, wherein the compound has the empirical formula(Cu_(1−z)Ag_(z))_(w)In_(x)Ga_(y)Al_(t)(ER¹)_(w(1−z))(ER²)_((w*z))(ER³)_(3x)(ER⁴)_(3y)(ER⁵)_(3t),w is from 0.7 to 1.25, z is from 0 to 1, x is from 0 to 1, y is from 0to 1, t is from 0 to 1, x plus y plus t is one, and wherein R¹, R², R³,R⁴ and R⁵ are defined the same as above.

A precursor compound of this disclosure may be a combination of xequivalents of Cu(ER), v*(1−y−t) equivalents of Ga(ER)₃, v*y equivalentsof In(ER)₃, v*t equivalents of Al(ER)₃, wherein the compound has theempirical formulaCu_(x)(Ga_(1−y−t)In_(y)Al_(t))_(v)((S_(1−z)Se_(z))R)_(w), wherein x isfrom 0.5 to 1.5, y is from 0 to 1, t is from 0 to 1, the sum of y plus tis from 0 to 1, z is from 0 to 1, v is from 0.5 to 1.5, w is from 2 to6, and R represents R groups, of which there are w in number, and areindependently selected from alkyl, aryl, heteroaryl, alkenyl, amido,silyl, and inorganic and organic ligands.

A precursor compound of this disclosure may be a combination of xequivalents of Cu(ER), v*(1−y−t) equivalents of Ga(ER)₃, v*y equivalentsof In(ER)₃, v*t equivalents of Al(ER)₃, wherein the compound has theempirical formulaCu_(x)(Ga_(1−y−t)In_(y)Al_(t))_(v)((S_(1−z)Se_(z))R)_(w), wherein x isfrom 0.5 to 1.5, y is from 0 to 1, t is from 0 to 1, the sum of y plus tis from 0 to 1, z is from 0 to 1, v is from 0.7 to 1.25, w is from 2 to6, and R represents R groups, of which there are w in number, and areindependently selected from alkyl, aryl, heteroaryl, alkenyl, amido,silyl, and inorganic and organic ligands.

In some embodiments, a precursor compound can be a combination of zequivalents of Cu(ER¹), x equivalents of Ga(ER³)₃, y equivalents ofIn(ER⁴)₃, t equivalents of Al(ER⁵)₃, wherein the compound has theempirical formulaCu_(z)In_(x)Ga_(y)Al_(t)(ER¹)_(w(1−z))(ER²)_((w*z))(ER³)_(3x)(ER⁴)_(3y)(ER⁵)_(3t),z is from 0.5 to 1.5, x is from 0 to 1, y is from 0 to 1, t is from 0 to1, x plus y plus t is one, and wherein R¹, R², R³, R⁴ and R⁵ are thesame as defined above.

In some embodiments, a precursor compound can be a combination of zequivalents of Cu(ER¹), x equivalents of Ga(ER³)₃, y equivalents ofIn(ER⁴)₃, t equivalents of Al(ER⁵)₃, wherein the compound has theempirical formulaCu_(z)In_(x)Ga_(y)Al_(t)(ER¹)_(w(1−z))(ER²)_((w*z))(ER³)_(3x)(ER⁴)_(3y)(ER⁵)_(3t),z is from 0.7 to 1.25, x is from 0 to 1, y is from 0 to 1, t is from 0to 1, x plus y plus t is one, and wherein R¹, R², R³, R⁴ and R⁵ are thesame as defined above.

In further aspects, a mixture of polymeric precursor compounds mayadvantageously be prepared with any desired stoichiometry with respectto the number of different Group 13 elements and their respectiveratios.

As shown in Reaction Scheme 12, a polymeric precursor compound may beprepared by contacting x equivalents of M^(B1)(ER¹)₃, y equivalents ofM^(B2)(ER²)₃, and z equivalents of M^(A)(ER³), where M^(B1) and M^(B2)are different atoms of Group 13, x is from 0.5 to 1.5, y is from 0.5 to1.5, and z is from 0.5 to 1.5, where it is to be understood that M^(B1)and M^(B2) can each be a mixture of Ga, In and Al, and M^(A) can be amixture of Cu and Ag. A polymeric precursor compound may have theempirical formula(Cu_(1−z)Ag_(z))_(w)In_(x)Ga_(y)Al_(t)(ER¹)_(w(1−z))(ER²)_((w*z))(ER³)_(3x)(ER⁴)_(3y)(ER⁵)_(3t).

Crosslinking Polymeric Precursors

Embodiments of this invention encompass methods and compositions forcrosslinking polymeric precursors and compositions.

In some aspects, a crosslinked polymeric precursor may be used tocontrol the viscosity of a precursor composition, or a polymericprecursor ink composition. The crosslinking of a polymeric precursor canincrease its molecular weight. The molecular weight of a polymericprecursor can be varied over a wide range by incorporating crosslinkinginto the preparation of the precursor. The viscosity of an inkcomposition can be varied over a wide range by using a crosslinkedprecursor to prepare an ink composition.

In some embodiments, the crosslinking of a polymeric precursorcomposition may be used to control the viscosity of the composition, orof a polymeric precursor ink composition. A polymeric precursorcomponent of a composition can be crosslinked by adding a crosslinkingagent to the composition. The viscosity of an ink composition may bevaried over a wide range by adding a crosslinking agent to the inkcomposition.

In further aspects, the crosslinking of a polymeric precursorcomposition may be used to control the variation of properties of thinfilms made with the precursor.

Examples of a crosslinking agent include E(Si(CH₃)₃)₂, where E is asdefined above, which can link polymer chains via an M-E-M crosslink.

Examples of a crosslinking agent include HEREH, M^(A)(ERE)H andM^(A)(ERE)M^(A), where M^(A), E, and R are as defined above.

A crosslinking agent can be made by reacting Cu₂O with HEREH to formCu(ERE)H or Cu(ERE)Cu.

Examples of a crosslinking agent include dithiols and diselenols, forexample, HER′EH, where E and R are as defined above. A diselenol canreact with two ER groups of different polymeric precursor chains to linkthe chains together.

An example of crosslinking using HER′EH is shown in Reaction Scheme 14.In Reaction Scheme 14, two chains of a polymeric precursor are linked bythe diselenol with elimination of 2 HER.

In another example, Cu(ER′E)Cu can be used during synthesis of apolymeric precursor to form crosslinks.

Embodiments of this invention may further provide a crosslinking agenthaving the formula (RE)₂M¹³(ER′E)M¹³(ER)₂, where M¹³, E, R′ and R are asdefined above. A crosslinking agent of this kind may be used eitherduring synthesis of a polymeric precursor to form crosslinks, or information of an ink or other composition.

In some embodiments, a polymeric precursor may incorporate crosslinkablefunctional groups. A crosslinkable functional group may be attached to aportion of the R groups of one or more kinds in the polymeric precursor.

Examples of crosslinkable functional groups include vinyl,vinylacrylate, epoxy, and cycloaddition and Diels-Alder reactive pairs.Crosslinking may be performed by methods known in the art including theuse of heat, light or a catalyst, as well as by vulcanization withelemental sulfur.

Dopants

In some embodiments, a polymeric precursor composition may include adopant. A dopant may be introduced into a polymeric precursor in thesynthesis of the precursor, or alternatively, can be added to acomposition or ink containing the polymeric precursor. A semiconductormaterial or thin film of this disclosure made from a polymeric precursormay contain atoms of one or more dopants. Methods for introducing adopant into a photovoltaic absorber layer include preparing the absorberlayer with a polymeric precursor of this invention containing thedopant.

The quantity of a dopant in an embodiment of this disclosure can be fromabout 1×10⁻⁷ atom percent to about 5 atom percent relative to the mostabundant Group 11 atom, or greater. In some embodiments, a dopant can beincluded at a level of from about 1×10¹⁶ cm⁻³ to about 1×10²¹ cm⁻³. Adopant can be included at a level of from about 1 ppm to about 10,000ppm.

In some embodiments, a dopant may be an alkali metal atom including Li,Na, K, Rb, and a mixture of any of the foregoing.

Embodiments of this invention may further include a dopant being analkaline earth metal atom including Be, Mg, Ca, Sr, Ba, and a mixture ofany of the foregoing.

In some embodiments, a dopant may be a transition metal atom from Group3 through Group 12.

In some embodiments, a dopant may be a transition metal atom from Group5 including V, Nb, Ta, and a mixture of any of the foregoing.

In some embodiments, a dopant may be a transition metal atom from Group6 including Cr, Mo, W, and a mixture of any of the foregoing.

In some embodiments, a dopant may be a transition metal atom from Group10 including Ni, Pd, Pt, and a mixture of any of the foregoing.

In some embodiments, a dopant may be a transition metal atom from Group12 including Zn, Cd, Hg, and a mixture of any of the foregoing.

In some embodiments, a dopant may be an atom from Group 14 including C,Si, Ge, Sn, Pb, and a mixture of any of the foregoing.

In some embodiments, a dopant may be an atom from Group 15 including P,As, Sb, Bi, and a mixture of any of the foregoing.

In some aspects, a polymeric precursor composition may advantageously beprepared to incorporate alkali metal ions as dopants. For example, apolymeric precursor composition may be prepared using an amount ofNa(ER), where E is S or Se and R is alkyl or aryl. In certainembodiments, a polymeric precursor composition may be prepared using anamount of NaIn(ER)₄, NaGa(ER)₄, LiIn(ER)₄, LiGa(ER)₄, KIn(ER)₄,KGa(ER)₄, or mixtures thereof, where E is S or Se and R is alkyl oraryl. A polymeric precursor compound of this kind can be used to controlthe level of alkali metal ions.

A dopant may be provided in a precursor as a counterion or introducedinto a thin film by any of the deposition methods described herein. Adopant may also be introduced into a thin film by methods known in theart including ion implantation.

A dopant of this disclosure may be p-type or n-type.

Any of the foregoing dopants may be used in an ink of this invention.

Capping Compounds

In some embodiments, a polymeric precursor composition may be formed asshown in Reaction Schemes 1 through 6, where one or more cappingcompounds are added to the reactions. A capping compound may control theextent of polymer chain formation. A capping compound may also be usedto control the viscosity of an ink containing the polymeric precursorcompound or composition, as well as its solubility and ability to from asuspension. Examples of capping compounds include inorganic ororganometallic complexes which bind to repeating units A or B, or both,and prevent further chain propagation. Examples of capping compoundsinclude R₂M^(B)ER, and RM^(B)(ER)₂.

Ligands

As used herein, the term ligand refers to any atom or chemical moietythat can donate electron density in bonding or coordination.

A ligand can be monodentate, bidentate or multidentate.

As used herein, the term ligand includes Lewis base ligands.

As used herein, the term organic ligand refers to an organic chemicalgroup composed of atoms of carbon and hydrogen, having from 1 to 22carbon atoms, and optionally containing oxygen, nitrogen, sulfur orother atoms, which can bind to another atom or molecule through a carbonatom. An organic ligand can be branched or unbranched, substituted orunsubstituted.

As used herein, the term inorganic ligand refers to an inorganicchemical group which can bind to another atom or molecule through anon-carbon atom.

Examples of ligands include halogens, water, alcohols, ethers,hydroxyls, amides, carboxylates, chalcogenylates, thiocarboxylates,selenocarboxylates, tellurocarboxylates, carbonates, nitrates,phosphates, sulfates, perchlorates, oxalates, and amines.

As used herein, the term chalcogenylate refers to thiocarboxylate,selenocarboxylate, and tellurocarboxylate, having the formula RCE₂ ⁻,where E is S, Se, or Te.

As used herein, the term chalcocarbamate refers to thiocarbamate,selenocarbamate, and tellurocarbamate, having the formula R¹R²NCE2,where E is S, Se, or Te, and R¹ and R² are the same or different and arehydrogen, alkyl, aryl, or an organic ligand.

Examples of ligands include F⁻, Cl⁻, H₂O, ROH, R₂O, OH⁻, RO⁻, NR₂ ⁻,RCO₂ ⁻, RCE₂ ⁻, CO₃ ²⁻, NO₃ ⁻, PO₄ ³⁻, SO₄ ²⁻, ClO₄ ⁻, C₂O₄ ²⁻, NH₃,NR₃, R₂NH, and RNH₂, where R is alkyl, and E is chalcogen.

Examples of ligands include azides, heteroaryls, thiocyanates,arylamines, arylalkylamines, nitrites, and sulfites.

Examples of ligands include Br⁻, N₃ ⁻, pyridine, [SCN—]⁻, ArNH₂, NO₂ ⁻,and SO₃ ²⁻ where Ar is aryl.

Examples of ligands include cyanides or nitriles, isocyanides orisonitriles, alkylcyanides, alkylnitriles, alkylisocyanides,alkylisonitriles, arylcyanides, arylnitriles, arylisocyanides, andarylisonitriles.

Examples of ligands include hydrides, carbenes, carbon monoxide,isocyanates, isonitriles, thiolates, alkylthiolates, dialkylthiolates,thioethers, thiocarbamates, phosphines, alkylphosphines, arylphosphines,arylalkylphosphines, arsenines, alkylarsenines, arylarsenines,arylalkylarsenines, stilbines, alkylstilbines, arylstilbines, andarylalkylstilbines.

Examples of ligands include I⁻, H⁻, R⁻, —CN⁻, —CO, RNC, RSH, R₂S, RS⁻,—SCN⁻, R₃P, R₃As, R₃Sb, alkenes, and aryls, where each R isindependently alkyl, aryl, or heteroaryl.

Examples of ligands include trioctylphosphine, trimethylvinylsilane andhexafluoroacetylacetonate.

Examples of ligands include nitric oxide, silyls, alkylgermyls,arylgermyls, arylalkylgermyls, alkylstannyls, arylstannyls,arylalkylstannyls, selenocyanates, selenolates, alkylselenolates,dialkylselenolates, selenoethers, selenocarbamates, tellurocyanates,tellurolates, alkyltellurolates, dialkyltellurolates, telluroethers, andtellurocarbamates.

Examples of ligands include chalcogenates, thiothiolates,selenothiolates, thioselenolates, selenoselenolates, alkylthiothiolates, alkyl selenothiolates, alkyl thioselenolates, alkylselenoselenolates, aryl thiothiolates, aryl selenothiolates, arylthioselenolates, aryl selenoselenolates, arylalkyl thiothiolates,arylalkyl selenothiolates, arylalkyl thioselenolates, and arylalkylselenoselenolates.

Examples of ligands include selenoethers and telluroethers.

Examples of ligands include NO, O²⁻, NH_(n)R_(3−n), PH_(n)R_(3−n), SiR₃⁻, GeR₃ ⁻, SnR₃ ⁻, ⁻SR, ⁻SeR, ⁻TeR, ⁻SSR, ⁻SeSR, ⁻SSeR, ⁻SeSeR, and RCN,where n is from 1 to 3, and each R is independently alkyl or aryl.

As used herein, the term transition metals refers to atoms of Groups 3though 12 of the Periodic Table of the elements recommended by theCommission on the Nomenclature of Inorganic Chemistry and published inIUPAC Nomenclature of Inorganic Chemistry, Recommendations 2005.

Photovoltaic Absorber Layer Compositions

A polymeric precursor may be used to prepare a material for use indeveloping semiconductor products.

The polymeric precursors of this invention may advantageously be used inmixtures to prepare a material with controlled or predeterminedstoichiometric ratios of the metal atoms in the material.

In some aspects, processes for solar cells that avoid additionalsulfurization or selenization steps may advantageously use polymericprecursor compounds and compositions of this invention.

The absorber material may be either an n-type or a p-type semiconductor,when such compound is known to exist.

In some embodiments, one or more polymeric precursor compounds may beused to prepare a CAIGAS layer on a substrate, wherein the layer has theempirical formula(Cu_(1−x)Ag_(x))_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)(S_(1−z)Se_(z))_(w),where x is from 0 to 1, y is from 0 to 1, t is from 0 to 1, the sum of yplus t is from 0 to 1, z is from 0 to 1, u is from 0.5 to 1.5, v is from0.5 to 1.5, and w is from 1 to 3. In certain embodiments, t may be from0.001 to 1, or from 0.01 to 1, or from 0.02 to 1, or from 0.03 to 1, orfrom 0.04 to 1, or from 0.05 to 1, or from 0.07 to 1, or from 0.1 to 1,or from 0.2 to 1, or from 0.3 to 1, or from 0.4 to 1. In certainembodiments, x may be from 0.001 to 1, or from 0.01 to 1, or from 0.02to 1, or from 0.03 to 1, or from 0.05 to 1, or from 0.07 to 1, or from0.1 to 1, or from 0.2 to 1, or from 0.3 to 1. In certain embodiments, tmay be from 0.001 to 1 and x may be from 0.001 to 1, or t may be from0.01 to 1 and x may be from 0.01 to 1, or t may be from 0.02 to 1 and xmay be from 0.02 to 1, or t may be from 0.05 to 1 and x may be from 0.05to 1, or t may be from 0.1 to 1 and x may be from 0.1 to 1, or t may befrom 0.15 to 1 and x may be from 0.15 to 1, or t may be from 0.2 to 1and x may be from 0.2 to 1, or t may be from 0.3 to 1 and x may be from0.3 to 1, or t may be from 0.35 to 1 and x may be from 0.35 to 1.

In some embodiments, one or more polymeric precursor compounds may beused to prepare a CAIGAS layer on a substrate, wherein the layer has theempirical formula(Cu_(1−x)Ag_(x))_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)(S_(1−z)Se_(z))_(w),where x is from 0.001 to 0.999, y is from 0.001 to 0.999, t is from0.001 to 0.999, the sum of y plus t is from 0.002 to 0.999, z is from 0to 1, u is from 0.5 to 1.5, v is from 0.5 to 1.5, and w is from 1 to 3.

In some embodiments, one or more polymeric precursor compounds may beused to prepare a CAIGAS layer on a substrate, wherein the layer has theempirical formula(Cu_(1−x)Ag_(x))_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)(S_(1−z)Se_(z))_(w),where x is from 0.001 to 0.999, y is from 0.001 to 0.999, t is from0.001 to 0.999, the sum of y plus t is from 0.002 to 0.999, z is from 0to 1, u is from 0.7 to 1.2, v is from 0.9 to 1.1, and w is from 2.0 to2.4.

In some embodiments, one or more polymeric precursor compounds may beused to prepare a CAIGAS material having a quantity of Ag atoms of from1 to 37.5 mol %, or from 2 to 37.5 mol %, or from 3 to 37.5 mol %, orfrom 5 to 37.5 mol %, or from 7 to 37.5 mol %, or from 10 to 37.5 mol %,or from 12 to 37.5 mol %.

In some embodiments, one or more polymeric precursor compounds may beused to prepare a CAIGAS material having a quantity of Al atoms of from1 to 37.5 mol %, or from 2 to 37.5 mol %, or from 3 to 37.5 mol %, orfrom 5 to 37.5 mol %, or from 7 to 37.5 mol %, or from 10 to 37.5 mol %,or from 12 to 37.5 mol %.

In some embodiments, one or more polymeric precursor compounds may beused to prepare a CIGAS layer on a substrate, wherein the layer has theempirical formula(Cu)_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)(S_(1−z)Se_(z))_(w), where y is from0 to 1, t is from 0 to 1, the sum of y plus t is from 0 to 1, z is from0 to 1, u is from 0.5 to 1.5, v is from 0.5 to 1.5, and w is from 1 to3. In certain embodiments, t may be from 0.001 to 1, or from 0.01 to 1,or from 0.02 to 1, or from 0.03 to 1, or from 0.04 to 1, or from 0.05 to1, or from 0.07 to 1, or from 0.1 to 1, or from 0.15 to 1, or from 0.2to 1, or from 0.25 to 1, or from 0.3 to 1, or from 0.4 to 1.

In some embodiments, one or more polymeric precursor compounds may beused to prepare a CIGAS layer on a substrate, wherein the layer has theempirical formula(Cu)_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)(S_(1−z)Se_(z))_(w), where y is from0.001 to 0.999, t is from 0.001 to 0.999, the sum of y plus t is from0.002 to 0.999, z is from 0 to 1, u is from 0.5 to 1.5, v is from 0.5 to1.5, and w is from 1 to 3.

In some embodiments, one or more polymeric precursor compounds may beused to prepare a CIGAS layer on a substrate, wherein the layer has theempirical formula(Cu)_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)(S_(1−z)Se_(z))_(w), where y is from0.001 to 0.999, t is from 0.001 to 0.999, the sum of y plus t is from0.002 to 0.999, z is from 0 to 1, u is from 0.7 to 1.2, v is from 0.9 to1.1, and w is from 2 to 2.4.

In some embodiments, one or more polymeric precursor compounds may beused to prepare a CIGAS material having a quantity of Al atoms of from 1to 37.5 mol %, or from 2 to 37.5 mol %, or from 3 to 37.5 mol %, or from5 to 37.5 mol %, or from 7 to 37.5 mol %, or from 10 to 37.5 mol %, orfrom 12 to 37.5 mol %.

In some embodiments, one or more polymeric precursor compounds may beused to prepare an AIGAS layer on a substrate, wherein the layer has theempirical formula Ag_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)(S_(1−z)Se_(z))_(w),where y is from 0 to 1, t is from 0 to 1, the sum of y plus t is from 0to 1, z is from 0 to 1, u is from 0.5 to 1.5, v is from 0.5 to 1.5, andw is from 1 to 3. In certain embodiments, t may be from 0.001 to 1, orfrom 0.01 to 1, or from 0.02 to 1, or from 0.03 to 1, or from 0.04 to 1,or from 0.05 to 1, or from 0.07 to 1, or from 0.1 to 1, or from 0.2 to1, or from 0.3 to 1, or from 0.4 to 1.

In some embodiments, one or more polymeric precursor compounds may beused to prepare an AIGAS layer on a substrate, wherein the layer has theempirical formula Ag_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)(S_(1−z)Se_(z))_(w),where y is from 0.001 to 0.999, t is from 0.001 to 0.999, the sum of yplus t is from 0.002 to 0.999, z is from 0 to 1, u is from 0.5 to 1.5, vis from 0.5 to 1.5, and w is from 1 to 3.

In some embodiments, one or more polymeric precursor compounds may beused to prepare an AIGAS layer on a substrate, wherein the layer has theempirical formula Ag_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)(S_(1−z)Se_(z))_(w),where y is from 0.001 to 0.999, t is from 0.001 to 0.999, the sum of yplus t is from 0.002 to 0.999, z is from 0 to 1, u is from 0.7 to 1.2, vis from 0.9 to 1.1, and w is from 2 to 2.4.

In some embodiments, one or more polymeric precursor compounds may beused to prepare a AIGAS material having a quantity of Ag atoms of from 1to 37.5 mol %, or from 2 to 37.5 mol %, or from 3 to 37.5 mol %, or from5 to 37.5 mol %, or from 7 to 37.5 mol %, or from 10 to 37.5 mol %, orfrom 12 to 37.5 mol %.

In some embodiments, one or more polymeric precursor compounds may beused to prepare a AIGAS material having a quantity of Al atoms of from 1to 37.5 mol %, or from 2 to 37.5 mol %, or from 3 to 37.5 mol %, or from5 to 37.5 mol %, or from 7 to 37.5 mol %, or from 10 to 37.5 mol %, orfrom 12 to 37.5 mol %.

Embodiments of this invention may further provide polymeric precursorsthat can be used to prepare a CAIGAS, CIGAS or AIGAS material for asolar cell product.

In some aspects, one or more polymeric precursors may be used to preparea CAIGAS, CIGAS or AIGAS material as a chemically and physically uniformlayer.

In some variations, one or more polymeric precursors may be used toprepare a CAIGAS, CIGAS or AIGAS material wherein the stoichiometry ofthe metal atoms of the material can be controlled.

In certain variations, one or more polymeric precursors may be used toprepare a CAIGAS, CIGAS or AIGAS material using nanoparticles preparedwith the polymeric precursors.

In certain embodiments, one or more polymeric precursors may be used toprepare a CAIGAS, CIGAS or AIGAS material as a layer that may beprocessed at relatively low temperatures to achieve a solar cell.

In some variations, one or more polymeric precursors may be used toprepare a chemically and physically uniform semiconductor CAIGAS, CIGASor AIGAS layer on a variety of substrates, including flexiblesubstrates.

Examples of an absorber material include CuAgInGaAlSSe, CuAgInGaAlSeTe,and CuAgInGaAlSTe.

A CAIGAS, CIGAS or AIGAS layer may be used with various junctionpartners to produce a solar cell. Examples of junction partner layersare known in the art and include CdS, ZnS, ZnSe, and CdZnS. See, forexample, Martin Green, Solar Cells: Operating Principles, Technology andSystem Applications (1986); Richard H. Bube, Photovoltaic Materials(1998); Antonio Luque and Steven Hegedus, Handbook of PhotovoltaicScience and Engineering (2003).

In some aspects, the thickness of an absorber layer may be from about0.001 to about 100 micrometers, or from about 0.001 to about 20micrometers, or from about 0.01 to about 10 micrometers, or from about0.05 to about 5 micrometers, or from about 0.1 to about 4 micrometers,or from about 0.1 to about 3.5 micrometers, or from about 0.1 to about 3micrometers, or from about 0.1 to about 2.5 micrometers.

Substrates

The polymeric precursors of this invention can be used to form a layeron a substrate. The substrate can be made of any substance, and can haveany shape. Substrate layers of polymeric precursors can be used tocreate a photovoltaic layer or device.

Examples of substrates on which a polymeric precursor of this disclosurecan be deposited or printed include semiconductors, dopedsemiconductors, silicon, gallium arsenide, insulators, glass, molybdenumglass, silicon dioxide, titanium dioxide, zinc oxide, silicon nitride,and combinations thereof.

A substrate may be coated with molybdenum or a molybdenum-containingcompound.

In some embodiments, a substrate may be pre-treated with amolybdenum-containing compound, or one or more compounds containingmolybdenum and selenium.

Examples of substrates on which a polymeric precursor of this disclosurecan be deposited or printed include metals, metal foils, molybdenum,aluminum, beryllium, cadmium, cerium, chromium, cobalt, copper, gallium,gold, lead, manganese, nickel, palladium, platinum, rhenium, rhodium,silver, stainless steel, steel, iron, strontium, tin, titanium,tungsten, zinc, zirconium, metal alloys, metal silicides, metalcarbides, and combinations thereof.

Examples of substrates on which a polymeric precursor of this disclosurecan be deposited or printed include polymers, plastics, conductivepolymers, copolymers, polymer blends, polyethylene terephthalates,polycarbonates, polyesters, polyester films, mylars, polyvinylfluorides, polyvinylidene fluoride, polyethylenes, polyetherimides,polyethersulfones, polyetherketones, polyimides, polyvinylchlorides,acrylonitrile butadiene styrene polymers, silicones, epoxys, andcombinations thereof.

Examples of substrates on which a polymeric precursor of this disclosurecan be deposited or printed include roofing materials.

Examples of substrates on which a polymeric precursor of this disclosurecan be deposited or printed include papers and coated papers.

A substrate of this disclosure can be of any shape. Examples ofsubstrates on which a polymeric precursor of this disclosure can bedeposited include a shaped substrate including a tube, a cylinder, aroller, a rod, a pin, a shaft, a plane, a plate, a blade, a vane, acurved surface or a spheroid.

A substrate may be layered with an adhesion promoter before thedeposition, coating or printing of a layer of a polymeric precursor ofthis invention.

Examples of adhesion promoters include a glass layer, a metal layer, atitanium-containing layer, a tungsten-containing layer, atantalum-containing layer, tungsten nitride, tantalum nitride, titaniumnitride, titanium nitride silicide, tantalum nitride silicide, achromium-containing layer, a vanadium-containing layer, a nitride layer,an oxide layer, a carbide layer, and combinations thereof.

Examples of adhesion promoters include organic adhesion promoters suchas organofunctional silane coupling agents, silanes,hexamethyldisilazanes, glycol ether acetates, ethylene glycolbis-thioglycolates, acrylates, acrylics, mercaptans, thiols, selenols,tellurols, carboxylic acids, organic phosphoric acids, triazoles, andmixtures thereof.

Substrates may be layered with a barrier layer before the deposition ofprinting of a layer of a polymeric precursor of this invention.

Examples of a barrier layer include a glass layer, a metal layer, atitanium-containing layer, a tungsten-containing layer, atantalum-containing layer, tungsten nitride, tantalum nitride, titaniumnitride, titanium nitride silicide, tantalum nitride silicide, andcombinations thereof.

A substrate can be of any thickness, and can be from about 20micrometers to about 20,000 micrometers or more in thickness.

Ink Compositions

Embodiments of this invention further provide ink compositions whichcontain one or more polymeric precursor compounds. The polymericprecursors of this invention may be used to make photovoltaic materialsby printing an ink onto a substrate.

An ink of this disclosure advantageously allows precise control of thestoichiometric ratios of certain atoms in the ink because the ink can becomposed of a mixture of polymeric precursors.

Inks of this disclosure can be made by any methods known in the art.

In some embodiments, an ink can be made by mixing a polymeric precursorwith one or more carriers. The ink may be a suspension of the polymericprecursors in an organic carrier. In some variations, the ink is asolution of the polymeric precursors in an organic carrier. The carriercan be an organic liquid or solution.

An ink can be made by providing one or more polymeric precursorcompounds and solubilizing, dissolving, solvating, or dispersing thecompounds with one or more carriers. The compounds dispersed in acarrier may be nanocrystalline, nanoparticles, microparticles,amorphous, or dissolved molecules.

The concentration of the polymeric precursors in an ink of thisdisclosure can be from about 0.001% to about 99% (w/w), or from about0.001% to about 90%, or from about 0.1% to about 90%.

A polymeric precursor may exist in a liquid or flowable phase under thetemperature and conditions used for deposition, coating or printing.

In some variations of this invention, polymeric precursors that arepartially soluble, or are insoluble in a particular carrier can bedispersed in the carrier by high shear mixing.

As used herein, the term dispersing encompasses the terms solubilizing,dissolving, and solvating.

The carrier for an ink of this disclosure may be an organic liquid orsolvent. Examples of a carrier for an ink of this disclosure include oneor more organic solvents, which may contain an aqueous component.

Embodiments of this invention further provide polymeric precursorcompounds having enhanced solubility in one or more carriers forpreparing inks. The solubility of a polymeric precursor compound can beselected by variation of the nature and molecular size and weight of oneor more organic ligands attached to the compound.

An ink composition of this invention may contain any of the dopantsdisclosed herein, or a dopant known in the art.

Ink compositions of this disclosure can be made by methods known in theart, as well as methods disclosed herein.

Examples of a carrier for an ink of this disclosure include alcohol,methanol, ethanol, isopropyl alcohol, thiols, butanol, butanediol,glycerols, alkoxyalcohols, glycols, 1-methoxy-2-propanol, acetone,ethylene glycol, propylene glycol, propylene glycol laurate, ethyleneglycol ethers, diethylene glycol, triethylene glycol monobutylether,propylene glycol monomethylether, 1,2-hexanediol, ethers, diethyl ether,aliphatic hydrocarbons, aromatic hydrocarbons, pentane, hexane, heptane,octane, isooctane, decane, cyclohexane, p-xylene, m-xylene, o-xylene,benzene, toluene, xylene, tetrahydrofuran, 2-methyltetrahydrofuran,siloxanes, cyclosiloxanes, silicone fluids, halogenated hydrocarbons,dibromomethane, dichloromethane, dichloroethane, trichloroethanechloroform, methylene chloride, acetonitrile, esters, acetates, ethylacetate, butyl acetate, acrylates, isobornyl acrylate, 1,6-hexanedioldiacrylate, polyethylene glycol diacrylate, ketones, acetone, methylethyl ketone, cyclohexanone, butyl carbitol, cyclopentanone, lactams,N-methylpyrrolidone, N-(2-hydroxyethyl)-pyrrolidone, cyclic acetals,cyclic ketals, aldehydes, amides, dimethylformamide, methyl lactate,oils, natural oils, terpenes, and mixtures thereof.

An ink of this disclosure may further include components such as asurfactant, a dispersant, an emulsifier, an anti-foaming agent, a dryer,a filler, a resin binder, a thickener, a viscosity modifier, ananti-oxidant, a flow agent, a plasticizer, a conductivity agent, acrystallization promoter, an extender, a film conditioner, an adhesionpromoter, and a dye. Each of these components may be used in an ink ofthis disclosure at a level of from about 0.001% to about 10% or more ofthe ink composition.

Examples of surfactants include siloxanes, polyalkyleneoxide siloxanes,polyalkyleneoxide polydimethylsiloxanes, polyesterpolydimethylsiloxanes, ethoxylated nonylphenols, nonylphenoxypolyethyleneoxyethanol, fluorocarbon esters, fluoroaliphatic polymericesters, fluorinated esters, alkylphenoxy alkyleneoxides, cetyl trimethylammonium chloride, carboxymethylamylose, ethoxylated acetylene glycols,betaines, N-n-dodecyl-N,N-dimethylbetaine, dialkyl sulfosuccinate salts,alkylnaphthalenesulfonate salts, fatty acid salts, polyoxyethylenealkylethers, polyoxyethylene alkylallylethers,polyoxyethylene-polyoxypropylene block copolymers, alkylamine salts,quaternary ammonium salts, and mixtures thereof.

Examples of surfactants include anionic, cationic, amphoteric, andnonionic surfactants. Examples of surfactants include SURFYNOL, DYNOL,ZONYL, FLUORAD, and SILWET surfactants.

A surfactant may be used in an ink of this disclosure at a level of fromabout 0.001% to about 2% of the ink composition.

Examples of a dispersant include a polymer dispersant, a surfactant,hydrophilic-hydrophobic block copolymers, acrylic block copolymers,acrylate block copolymers, graft polymers, and mixtures thereof.

Examples of an emulsifier include a fatty acid derivative, an ethylenestearamide, an oxidized polyethylene wax, mineral oils, apolyoxyethylene alkyl phenol ether, a polyoxyethylene glycol ether blockcopolymer, a polyoxyethylene sorbitan fatty acid ester, a sorbitan, analkyl siloxane polyether polymer, polyoxyethylene monostearates,polyoxyethylene monolaurates, polyoxyethylene monooleates, and mixturesthereof.

Examples of an anti-foaming agent include polysiloxanes,dimethylpolysiloxanes, dimethyl siloxanes, silicones, polyethers, octylalcohol, organic esters, ethyleneoxide propyleneoxide copolymers, andmixtures thereof.

Examples of a dryer include aromatic sulfonic acids, aromatic carboxylicacids, phthalic acid, hydroxyisophthalic acid, N-phthaloylglycine,2-Pyrrolidone 5-carboxylic acid, and mixtures thereof.

Examples of a filler include metallic fillers, silver powder, silverflake, metal coated glass spheres, graphite powder, carbon black,conductive metal oxides, ethylene vinyl acetate polymers, and mixturesthereof.

Examples of a resin binder include acrylic resins, alkyd resins, vinylresins, polyvinyl pyrrolidone, phenolic resins, ketone resins, aldehyderesins, polyvinyl butyral resin, amide resins, amino resins,acrylonitrile resins, cellulose resins, nitrocellulose resins, rubbers,fatty acids, epoxy resins, ethylene acrylic copolymers, fluoropolymers,gels, glycols, hydrocarbons, maleic resins, urea resins, naturalrubbers, natural gums, phenolic resins, cresols, polyamides,polybutadienes, polyesters, polyolefins, polyurethanes, isocynates,polyols, thermoplastics, silicates, silicones, polystyrenes, andmixtures thereof.

Examples of thickeners and viscosity modifiers include conductingpolymers, celluloses, urethanes, polyurethanes, styrene maleic anhydridecopolymers, polyacrylates, polycarboxylic acids, carboxymethylcelluoses,hydroxyethylcelluloses, methylcelluloses, methyl hydroxyethylcelluloses, methyl hydroxypropyl celluloses, silicas, gellants,aluminates, titanates, gums, clays, waxes, polysaccharides, starches,and mixtures thereof.

Examples of anti-oxidants include phenolics, phosphites, phosphonites,thioesters, stearic acids, ascorbic acids, catechins, cholines, andmixtures thereof.

Examples of flow agents include waxes, celluloses, butyrates,surfactants, polyacrylates, and silicones.

Examples of a plasticizer include alkyl benzyl phthalates, butyl benzylphthalates, dioctyl phthalates, diethyl phthalates, dimethyl phthalates,di-2-ethylhexy-adipates, diisobutyl phthalates, diisobutyl adipates,dicyclohexyl phthalates, glycerol tribenzoates, sucrose benzoates,polypropylene glycol dibenzoates, neopentyl glycol dibenzoates, dimethylisophthalates, dibutyl phthalates, dibutyl sebacates,tri-n-hexyltrimellitates, and mixtures thereof.

Examples of a conductivity agent include lithium salts, lithiumtrifluoromethanesulfonates, lithium nitrates, dimethylaminehydrochlorides, diethylamine hydrochlorides, hydroxylaminehydrochlorides, and mixtures thereof.

Examples of a crystallization promoter include copper chalcogenides,alkali metal chalcogenides, alkali metal salts, alkaline earth metalsalts, sodium chalcogenates, cadmium salts, cadmium sulfates, cadmiumsulfides, cadmium selenides, cadmium tellurides, indium sulfides, indiumselenides, indium tellurides, gallium sulfides, gallium selenides,gallium tellurides, molybdenum, molybdenum sulfides, molybdenumselenides, molybdenum tellurides, molybdenum-containing compounds, andmixtures thereof.

An ink may contain one or more components selected from the group of aconducting polymer, silver metal, silver selenide, silver sulfide,copper metal, indium metal, gallium metal, zinc metal, alkali metals,alkali metal salts, alkaline earth metal salts, sodium chalcogenates,calcium chalcogenates, cadmium sulfide, cadmium selenide, cadmiumtelluride, indium sulfide, indium selenide, indium telluride, galliumsulfide, gallium selenide, gallium telluride, zinc sulfide, zincselenide, zinc telluride, copper sulfide, copper selenide, coppertelluride, molybdenum sulfide, molybdenum selenide, molybdenumtelluride, and mixtures of any of the foregoing.

An ink of this disclosure may contain particles of a metal, a conductivemetal, or an oxide. Examples of metal and oxide particles includesilica, alumina, titania, copper, iron, steel, aluminum and mixturesthereof.

In certain variations, an ink may contain a biocide, a sequesteringagent, a chelator, a humectant, a coalescent, or a viscosity modifier.

In certain aspects, an ink of this disclosure may be formed as asolution, a suspension, a slurry, or a semisolid gel or paste. An inkmay include one or more polymeric precursors solubilized in a carrier,or may be a solution of the polymeric precursors. In certain variations,a polymeric precursor may include particles or nanoparticles that can besuspended in a carrier, and may be a suspension or paint of thepolymeric precursors. In certain embodiments, a polymeric precursor canbe mixed with a minimal amount of a carrier, and may be a slurry orsemisolid gel or paste of the polymeric precursor.

The viscosity of an ink of this disclosure can be from about 0.5centipoises (cP) to about 50 cP, or from about 0.6 to about 30 cP, orfrom about 1 to about 15 cP, or from about 2 to about 12 cP.

The viscosity of an ink of this disclosure can be from about 20 cP toabout 2×10⁶ cP, or greater. The viscosity of an ink of this disclosurecan be from about 20 cP to about 1×10⁶ cP, or from about 200 cP to about200,000 cP, or from about 200 cP to about 100,000 cP, or from about 200cP to about 40,000 cP, or from about 200 cP to about 20,000 cP.

The viscosity of an ink of this disclosure can be about 1 cP, or about 2cP, or about 5 cP, or about 20 cP, or about 100 cP, or about 500 cP, orabout 1,000 cP, or about 5,000 cP, or about 10,000 cP, or about 20,000cP, or about 30,000 cP, or about 40,000 cP.

In some embodiments, an ink may contain one or more components from thegroup of a surfactant, a dispersant, an emulsifier, an anti-foamingagent, a dryer, a filler, a resin binder, a thickener, a viscositymodifier, an anti-oxidant, a flow agent, a plasticizer, a conductivityagent, a crystallization promoter, an extender, a film conditioner, anadhesion promoter, and a dye. In certain variations, an ink may containone or more compounds from the group of cadmium sulfide, cadmiumselenide, cadmium telluride, zinc sulfide, zinc selenide, zinctelluride, copper sulfide, copper selenide, and copper telluride. Insome aspects, an ink may contain particles of a metal, a conductivemetal, or an oxide.

An ink may be made by dispersing one or more polymeric precursorcompounds of this disclosure in one or more carriers to form adispersion or solution.

A polymeric precursor ink composition can be prepared by dispersing oneor more polymeric precursors in a solvent, and heating the solvent todissolve or disperse the polymeric precursors. The polymeric precursorsmay have a concentration of from about 0.001% to about 99% (w/w), orfrom about 0.001% to about 90%, or from about 0.1% to about 90%, or fromabout 0.1% to about 50%, or from about 0.1% to about 40%, or from about0.1% to about 30%, or from about 0.1% to about 20%, or from about 0.1%to about 10% in the solution or dispersion.

Processes for Films of Polymeric Precursors on Substrates

The polymeric precursors of this invention can be used to makephotovoltaic materials by depositing a layer onto a substrate, where thelayer contains one or more polymeric precursors. The deposited layer maybe a film or a thin film. Substrates are described above.

As used herein, the terms “deposit,” “depositing,” and “deposition”refer to any method for placing a compound or composition onto a surfaceor substrate, including spraying, coating, and printing.

As used herein, the term “thin film” refers to a layer of atoms ormolecules, or a composition layer on a substrate having a thickness ofless than about 300 micrometers.

A deposited layer of this disclosure advantageously allows precisecontrol of the stoichiometric ratios of certain atoms in the layerbecause the layer can be composed of a mixture of polymeric precursors.

The polymeric precursors of this invention, and compositions containingpolymeric precursors, can be deposited onto a substrate using methodsknown in the art, as well as methods disclosed herein.

Examples of methods for depositing a polymeric precursor onto a surfaceor substrate include all forms of spraying, coating, and printing.

Solar cell layers can be made by depositing one or more polymericprecursors of this disclosure on a flexible substrate in a highthroughput roll process. The depositing of polymeric precursors in ahigh throughput roll process can be done by spraying or coating acomposition containing one or more polymeric precursors, or by printingan ink containing one or more polymeric precursors of this disclosure.

Examples of methods for depositing a polymeric precursor onto a surfaceor substrate include spraying, spray coating, spray deposition, spraypyrolysis, and combinations thereof.

Examples of methods for printing using an ink of this disclosure includescreen printing, inkjet printing, aerosol jet printing, ink printing,jet printing, stamp/pad printing, transfer printing, pad printing,flexographic printing, gravure printing, contact printing, reverseprinting, thermal printing, lithography, electrophotographic printing,and combinations thereof.

Examples of methods for depositing a polymeric precursor onto a surfaceor substrate include electrodepositing, electroplating, electrolessplating, bath deposition, coating, dip coating, wet coating, spincoating, knife coating, roller coating, rod coating, slot die coating,meyerbar coating, lip direct coating, capillary coating, liquiddeposition, solution deposition, layer-by-layer deposition, spincasting, and solution casting.

Examples of methods for depositing a polymeric precursor onto a surfaceor substrate include chemical vapor deposition, aerosol chemical vapordeposition, metal-organic chemical vapor deposition, organometallicchemical vapor deposition, plasma enhanced chemical vapor deposition,and combinations thereof.

Examples of methods for depositing a polymeric precursor onto a surfaceor substrate include atomic layer deposition, plasma-enhanced atomiclayer deposition, vacuum chamber deposition, sputtering, RF sputtering,DC sputtering, magnetron sputtering, evaporation, electron beamevaporation, laser ablation, gas-source polymeric beam epitaxy, vaporphase epitaxy, liquid phase epitaxy, and combinations thereof.

In certain embodiments, a first polymeric precursor may be depositedonto a substrate, and subsequently a second polymeric precursor may bedeposited onto the substrate. In certain embodiments, several differentpolymeric precursors may be deposited onto the substrate to create alayer.

In certain variations, different polymeric precursors may be depositedonto a substrate simultaneously, or sequentially, whether by spraying,coating, printing, or by other methods. The different polymericprecursors may be contacted or mixed before the depositing step, duringthe depositing step, or after the depositing step. The polymericprecursors can be contacted before, during, or after the step oftransporting the polymeric precursors to the substrate surface.

The depositing of polymeric precursors, including by spraying, coating,and printing, can be done in a controlled or inert atmosphere, such asin dry nitrogen and other inert gas atmospheres, as well as in a partialvacuum atmosphere.

Processes for depositing, spraying, coating, or printing polymericprecursors can be done at various temperatures including from about −20°C. to about 650° C., or from about −20° C. to about 600° C., or fromabout −20° C. to about 400° C., or from about 20° C. to about 360° C.,or from about 20° C. to about 300° C., or from about 20° C. to about250° C.

Processes for making a solar cell involving a step of transforming apolymeric precursor compound into a material or semiconductor can beperformed at various temperatures including from about 100° C. to about650° C., or from about 150° C. to about 650° C., or from about 250° C.to about 650° C., or from about 300° C. to about 650° C., or from about400° C. to about 650° C., or from about 300° C. to about 600° C., orfrom about 300° C. to about 550° C., or from about 300° C. to about 500°C., or from about 300° C. to about 450° C.

In certain aspects, depositing of polymeric precursors on a substratecan be done while the substrate is heated. In these variations, athin-film material may be deposited or formed on the substrate.

In some embodiments, a step of converting a precursor to a material anda step of annealing can be done simultaneously. In general, a step ofheating a precursor can be done before, during or after any step ofdepositing the precursor.

In some variations, a substrate can be cooled after a step of heating.In certain embodiments, a substrate can be cooled before, during, orafter a step of depositing a precursor. A substrate may be cooled toreturn the substrate to a lower temperature, or to room temperature, orto an operating temperature of a deposition unit. Various coolants orcooling methods can be applied to cool a substrate.

The depositing of polymeric precursors on a substrate may be done withvarious apparatuses and devices known in art, as well as devicesdescribed herein.

In some variations, the depositing of polymeric precursors can beperformed using a spray nozzle with adjustable nozzle dimensions toprovide a uniform spray composition and distribution.

Embodiments of this disclosure further contemplate articles made bydepositing a layer onto a substrate, where the layer contains one ormore polymeric precursors. The article may be a substrate having a layerof a film, or a thin film, which is deposited, sprayed, coated, orprinted onto the substrate. In certain variations, an article may have asubstrate printed with a polymeric precursor ink, where the ink isprinted in a pattern on the substrate.

Photovoltaic Devices

The polymeric precursors of this invention can be used to makephotovoltaic materials and solar cells of high efficiency.

As shown in FIG. 6, embodiments of this invention may further provideoptoelectronic devices and energy conversion systems. Following thesynthesis of polymeric precursor compounds, the compounds can besprayed, deposited, or printed onto substrates and formed into absorbermaterials and semiconductor layers. Absorber materials can be the basisfor optoelectronic devices and energy conversion systems.

In some embodiments, the solar cell is a thin layer solar cell having aCAIGAS, CIGAS or AIGAS absorber layer deposited or printed on asubstrate.

Embodiments of this invention may provide improved efficiency for solarcells used for light to electricity conversion.

In some embodiments, a solar cell of this disclosure is a heterojunctiondevice made with a CAIGAS, CIGAS or AIGAS cell. The CAIGAS, CIGAS orAIGAS layer may be used as a junction partner with a layer of, forexample, cadmium sulfide, cadmium selenide, cadmium telluride, zincsulfide, zinc selenide, or zinc telluride. The absorber layer may beadjacent to a layer of MgS, MgSe, MgTe, HgS, HgSe, HgTe, AlN, AlP, AlAs,AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, or combinationsthereof.

In certain variations, a solar cell of this disclosure is amultijunction device made with one or more stacked solar cells.

As shown in FIG. 7, a solar cell device of this disclosure may have asubstrate 10, an electrode layer 20, an absorber layer 30, a windowlayer 40, and a transparent conductive layer (TCO) 50. The substrate 10may be metal, plastic, glass, or ceramic. The electrode layer 20 can bea molybdenum-containing layer. The absorber layer 30 may be a CAIGSlayer. The window layer 40 may be a cadmium sulfide layer. Thetransparent conductive layer 50 can be an indium tin oxide layer or adoped zinc oxide layer.

A solar cell device of this disclosure may have a substrate, anelectrode layer, an absorber layer, a window layer, an adhesionpromoting layer, a junction partner layer, a transparent layer, atransparent electrode layer, a transparent conductive oxide layer, atransparent conductive polymer layer, a doped conductive polymer layer,an encapsulating layer, an anti-reflective layer, a protective layer, ora protective polymer layer. In certain variations, an absorber layerincludes a plurality of absorber layers.

In certain variations, solar cells may be made by processes usingpolymeric precursor compounds and compositions of this invention thatadvantageously avoid additional sulfurization or selenization steps.

In certain variations, a solar cell device may have amolybdenum-containing layer, or an interfacial molybdenum-containinglayer.

Examples of a protective polymer include silicon rubbers, butyrylplastics, ethylene vinyl acetates, and combinations thereof.

Substrates can be made of a flexible material which can be handled in aroll. The electrode layer may be a thin foil.

Absorber layers of this disclosure can be made by depositing or printinga composition containing nanoparticles onto a substrate, where thenanoparticles can be made with polymeric precursor compounds of thisinvention. In some processes, nanoparticles can be made with, or formedfrom polymeric precursor compounds and deposited on a substrate.Deposited nanoparticles can subsequently be transformed by theapplication of heat or energy.

In some embodiments, the absorber layer may be formed from nanoparticlesor semiconductor nanoparticles which have been deposited on a substrateand subsequently transformed by heat or energy.

In some embodiments, a thin film photovoltaic device may have atransparent conductor layer, a buffer layer, a p-type absorber layer, anelectrode layer, and a substrate. The transparent conductor layer may bea transparent conductive oxide (TCO) layer such as a zinc oxide layer,or zinc oxide layer doped with aluminum, or a carbon nanotube layer, ora tin oxide layer, or a tin oxide layer doped with fluorine, or anindium tin oxide layer, or an indium tin oxide layer doped withfluorine, while the buffer layer can be cadmium sulfide, or cadmiumsulfide and high resistivity zinc oxide. The p-type absorber layer canbe a CAIGAS, CIGAS or AIGAS layer, and the electrode layer can bemolybdenum. The transparent conductor layer can be up to about 0.5micrometers in thickness. The buffer layer can also be a cadmium sulfiden-type junction partner layer. In some embodiments, the buffer layer maybe a silicon dioxide, an aluminum oxide, a titanium dioxide, or a boronoxide.

Some examples of transparent conductive oxides are given in K. Ellmer etal., Transparent Conductive Zinc Oxide, Vol. 104, Springer Series inMaterials Science (2008).

In some aspects, a solar cell can include a molybdenum selenideinterface layer, which may be formed using various molybdenum-containingand selenium-containing compounds that can be added to an ink forprinting, or deposited onto a substrate.

A thin film material photovoltaic absorber layer can be made with one ormore polymeric precursors of this invention. For example, a polymericprecursor ink can be sprayed onto a stainless steel substrate using aspray pyrolysis unit in a glovebox in an inert atmosphere. The spraypyrolysis unit may have an ultrasonic nebulizer, precision flow metersfor inert gas carrier, and a tubular quartz reactor in a furnace. Thespray-coated substrate can be heated at a temperature of from about 25°C. to about 650° C. in an inert atmosphere, thereby producing a thinfilm material photovoltaic absorber layer.

In some examples, a thin film material photovoltaic absorber layer canbe made by providing a polymeric precursor ink which is filtered with a0.45 micron filter, or a 0.3 micron filter. The ink can be depositedonto an aluminum substrate using a spin casting unit in a glovebox ininert argon atmosphere. The substrate can be spin coated with thepolymeric precursor ink to a film thickness of about 0.1 to 5 microns.The substrate can be removed and heated at a temperature of from about100° C. to about 600° C., or from about 100° C. to about 650° C. in aninert atmosphere, thereby producing a thin film material photovoltaicabsorber layer.

In further examples, a thin film material photovoltaic absorber layercan be made by providing a polymeric precursor ink which is filteredwith a 0.45 micron filter, or a 0.3 micron filter. The ink may beprinted onto a polyethylene terephthalate substrate using a inkjetprinter in a glovebox in an inert atmosphere. A film of about 0.1 to 5microns thickness can be deposited on the substrate. The substrate canbe removed and heated at a temperature of from about 100° C. to about600° C., or from about 100° C. to about 650° C. in an inert atmosphere,thereby producing a thin film material photovoltaic absorber layer.

In some examples, a solar cell can be made by providing an electrodelayer on a polyethylene terephthalate substrate. A thin film materialphotovoltaic absorber layer can be coated onto the electrode layer asdescribed above. A window layer can be deposited onto the absorberlayer. A transparent conductive oxide layer can be deposited onto thewindow layer, thereby forming an embodiment of a solar cell.

Methods for making a photovoltaic absorber layer on a substrate includeproviding one or more polymeric precursor compounds, providing asubstrate, spraying the compounds onto the substrate, and heating thesubstrate at a temperature of from about 100° C. to about 600° C., or offrom about 100° C. to about 650° C. in an inert atmosphere, therebyproducing a photovoltaic absorber layer having a thickness of from 0.001to 100 micrometers. The spraying can be done in spray coating, spraydeposition, jet deposition, or spray pyrolysis. The substrate may beglass, metal, polymer, plastic, or silicon.

In certain variations, methods for making a photovoltaic absorber layermay include heating the compounds to a temperature of from about 20° C.to about 400° C. while depositing, spraying, coating, or printing thecompounds onto the substrate.

Methods for making a photovoltaic absorber layer on a substrate includeproviding one or more polymeric precursor compounds, providing asubstrate, depositing the compounds onto the substrate, and heating thesubstrate at a temperature of from about 100° C. to about 650° C., orfrom about 100° C. to about 600° C., or from about 100° C. to about 400°C., or from about 100° C. to about 300° C. in an inert atmosphere,thereby producing a photovoltaic absorber layer having a thickness offrom 0.001 to 100 micrometers. The depositing can be done inelectrodepositing, electroplating, electroless plating, bath deposition,liquid deposition, solution deposition, layer-by-layer deposition, spincasting, or solution casting. The substrate may be glass, metal,polymer, plastic, or silicon.

Methods for making a photovoltaic absorber layer on a substrate includeproviding one or more polymeric precursor inks, providing a substrate,printing the inks onto the substrate, and heating the substrate at atemperature of from about 100° C. to about 600° C., or from about 100°C. to about 650° C. in an inert atmosphere, thereby producing aphotovoltaic absorber layer having a thickness of from 0.001 to 100micrometers. The printing can be done in screen printing, inkjetprinting, transfer printing, flexographic printing, or gravure printing.The substrate may be glass, metal, polymer, plastic, or silicon. Themethod may further include adding to the ink an additionalindium-containing compound, such as In(SeR)₃, wherein R is alkyl oraryl.

Electrical Power Generation and Transmission

This disclosure contemplates methods for producing and deliveringelectrical power. A photovoltaic device of this invention can be used,for example, to convert solar light to electricity which can be providedto a commercial power grid.

As used herein, the term “solar cell” refers to individual solar cell aswell as a solar cell array, which can combine a number of solar cells.

The solar cell devices of this disclosure can have improved reliability.Solar cell devices can be manufactured in modular panels.

The power systems of this disclosure can be made in large or smallscale, including power for a personal use, as well as on a megawattscale for a public use.

An important feature of the solar cell devices and power systems of thisdisclosure is that they can be manufactured and used with lowenvironmental impact.

A power system of this disclosure may utilize a solar cell on a movablemounting, which may be motorized to face the solar cell toward thelight. Alternatively, a solar cell may be mounted on a fixed object inan optimal orientation.

Solar cells can be attached in panels in which various groups of cellsare electrically connected in series and in parallel to provide suitablevoltage and current characteristics.

Solar cells can be installed on rooftops, as well as outdoor, sunlightedsurfaces of all kinds Solar cells can be combined with various kinds ofroofing materials such as roofing tiles or shingles.

A power system can include a solar cell array and a battery storagesystem. A power system may have a diode-containing circuit and avoltage-regulating circuit to prevent the battery storage system fromdraining through the solar cells or from being overcharged.

A power system can be used to provide power for lighting, electricvehicles, electric buses, electric airplanes, pumping water,desalinization of water, refrigeration, milling, manufacturing, andother uses.

Sources of Elements

Sources of silver include silver metal, Ag(I), silver nitrates, silverhalides, silver chlorides, silver acetates, silver alkoxides, andmixtures thereof.

Sources of copper include copper metal, Cu(I), Cu(II), copper halides,copper chlorides, copper acetates, copper alkoxides, copper alkyls,copper diketonates, copper 2,2,6,6,-tetramethyl-3,5,-heptanedionate,copper 2,4-pentanedionate, copper hexafluoroacetylacetonate, copperacetylacetonate, copper dimethylaminoethoxide, copper ketoesters, andmixtures thereof.

Sources of indium include indium metal, trialkylindium,trisdialkylamineindium, indium halides, indium chlorides, dimethylindiumchlorides, trimethylindium, indium acetylacetonates, indiumhexafluoropentanedionates, indium methoxyethoxides, indiummethyltrimethylacetylacetates, indium trifluoropentanedionates, andmixtures thereof.

Sources of gallium include gallium metal, trialkylgallium,trisdialkylamine gallium, gallium halides, gallium fluorides, galliumchlorides, gallium iodides, diethylgallium chlorides, gallium acetate,gallium 2,4-pentanedionate, gallium ethoxide, gallium2,2,6,6,-tetramethylheptanedionate, trisdimethylaminogallium, andmixtures thereof.

Sources of aluminum include aluminum metal, trialkylaluminum,trisdialkylamine aluminum, aluminum halides, aluminum fluorides,aluminum chlorides, aluminum iodides, diethylaluminum chlorides,aluminum acetate, aluminum 2,4-pentanedionate, aluminum ethoxide,aluminum 2,2,6,6,-tetramethylheptanedionate, trisdimethylaminoaluminum,and mixtures thereof.

Some sources of gallium and indium are described in International PatentPublication No. WO2008057119.

Additional Sulfurization or Selenization

In various processes of this disclosure, a composition or material mayoptionally be subjected to a step of sulfurization or selenization.

Sulfurization with H₂S or selenization with H₂Se may be carried out byusing pure H₂S or H₂Se, respectively, or may be done by dilution inhydrogen or in nitrogen. Selenization can also be carried out with Sevapor, or other source of elemental selenium.

A sulfurization or selenization step can be done at any temperature fromabout 200° C. to about 650° C., or at temperatures below 200° C. One ormore steps of sulfurization and selenization may be performedconcurrently, or sequentially.

Examples of sulfurizing agents include hydrogen sulfide, hydrogensulfide diluted with hydrogen, elemental sulfur, sulfur powder, carbondisulfide, alkyl polysulfides, dimethyl sulfide, dimethyl disulfide, andmixtures thereof.

Examples of selenizing agents include hydrogen selenide, hydrogenselenide diluted with hydrogen, elemental selenium, selenium powder,carbon diselenide, alkyl polyselenides, dimethyl selenide, dimethyldiselenide, and mixtures thereof.

A sulfurization or selenization step can also be done with co-depositionof another metal such as copper, indium, or gallium.

Chemical Definitions

As used herein, the term (X,Y) when referring to compounds or atomsindicates that either X or Y, or a combination thereof may be found inthe formula. For example, (S,Se) indicates that atoms of either sulfuror selenium, or any combination thereof may be found. Further, usingthis notation the amount of each atom can be specified. For example,when appearing in the chemical formula of a molecule, the notation(0.75In,0.25 Ga) indicates that the atom specified by the symbols in theparentheses is indium in 75% of the compounds and gallium in theremaining 25% of the compounds, regardless of the identity any otheratoms in the compound. In the absence of a specified amount, the term(X,Y) refers to approximately equal amounts of X and Y.

The atoms S, Se, and Te of Group 16 are referred to as chalcogens.

As used herein, the letter “S” in CIGS, AIGS, CAIGS, CIGAS, AIGAS andCAIGAS refers to sulfur or selenium or both. The letter “C” in CIGS,CAIGS, CIGAS, and CAIGAS refers to copper. The letter “A” in AIGS,CAIGS, AIGAS and CAIGAS which appears before the letters I and G refersto silver. The letter “I” in CIGS, AIGS, CAIGS, CIGAS, AIGAS and CAIGASrefers to indium. The letter “G” in CIGS, AIGS, CAIGS, CIGAS, AIGAS andCAIGAS refers to gallium. The letter “A” in CIGAS, AIGAS and CAIGASwhich appears after the letters I and G refers to aluminum.

CAIGAS therefore could also be represented as Cu/Ag/In/Ga/Al/S/Se or(Cu,Ag)(In,Ga,Al)(S,Se).

As used herein, the terms CIGS, AIGS, and CAIGS include the variationsC(I,G)S, A(I,G)S, and CA(I,G)S, respectively, and CIS, AIS, and CAIS,respectively, as well as CGS, AGS, and CAGS, respectively, unlessdescribed otherwise.

The terms CIGAS, AIGAS and CAIGAS include the variations C(I,G,A)S,A(I,G,A)S, and CA(I,G,A)S, respectively, and CIGS, AIGS, and CAIGS,respectively, as well as CGAS, AGAS, and CAGAS, respectively, unlessdescribed otherwise.

The term CAIGAS refers to variations in which either C or Silver iszero, for example, AIGAS and CIGAS, respectively, as well as variationsin which Aluminum is zero, for example, CAIGS, AIGS, and CIGS.

As used herein, the term CIGS includes the terms CIGSSe and CIGSe, andthese terms refer to compounds or materials containingcopper/indium/gallium/sulfur/selenium, which may contain sulfur orselenium or both. The term AIGS includes the terms AIGSSe and AIGSe, andthese terms refer to compounds or materials containingsilver/indium/gallium/sulfur/selenium, which may contain sulfur orselenium or both. The term CAIGS includes the terms CAIGSSe and CAIGSe,and these terms refer to compounds or materials containingcopper/silver/indium/gallium/sulfur/selenium, which may contain sulfuror selenium or both.

As used herein, the term “chalcogenide” refers to a compound containingone or more chalcogen atoms bonded to one or more metal atoms.

The term “alkyl” as used herein refers to a hydrocarbyl radical of asaturated aliphatic group, which can be a branched or unbranched,substituted or unsubstituted aliphatic group containing from 1 to 22carbon atoms. This definition applies to the alkyl portion of othergroups such as, for example, cycloalkyl, alkoxy, alkanoyl, aralkyl, andother groups defined below. The term “cycloalkyl” as used herein refersto a saturated, substituted or unsubstituted cyclic alkyl ringcontaining from 3 to 12 carbon atoms. As used herein, the term“C(1-5)alkyl” includes C(1)alkyl, C(2)alkyl, C(3)alkyl, C(4)alkyl, andC(5)alkyl. Likewise, the term “C(3-22)alkyl” includes C(1)alkyl,C(2)alkyl, C(3)alkyl, C(4)alkyl, C(5)alkyl, C(6)alkyl, C(7)alkyl,C(8)alkyl, C(9)alkyl, C(10)alkyl, C(11)alkyl, C(12)alkyl, C(13)alkyl,C(14)alkyl, C(15)alkyl, C(16)alkyl, C(17)alkyl, C(18)alkyl, C(19)alkyl,C(20)alkyl, C(21)alkyl, and C(22)alkyl.

The term “alkenyl” as used herein refers to an unsaturated, branched orunbranched, substituted or unsubstituted alkyl or cycloalkyl having 2 to22 carbon atoms and at least one carbon-carbon double bond. The term“alkynyl” as used herein refers to an unsaturated, branched orunbranched, substituted or unsubstituted alkyl or cycloalkyl having 2 to22 carbon atoms and at least one carbon-carbon triple bond.

The term “alkoxy” as used herein refers to an alkyl, cycloalkyl,alkenyl, or alkynyl group covalently bonded to an oxygen atom. The term“alkanoyl” as used herein refers to —C(═O)-alkyl, which mayalternatively be referred to as “acyl.” The term “alkanoyloxy” as usedherein refers to —O—C(═O)-alkyl groups. The term “alkylamino” as usedherein refers to the group —NRR′, where R and R′ are each eitherhydrogen or alkyl, and at least one of R and R′ is alkyl. Alkylaminoincludes groups such as piperidino wherein R and R′ form a ring. Theterm “alkylaminoalkyl” refers to -alkyl-NRR′.

The term “aryl” as used herein refers to any stable monocyclic,bicyclic, or polycyclic carbon ring system of from 4 to 12 atoms in eachring, wherein at least one ring is aromatic. Some examples of an arylinclude phenyl, naphthyl, tetrahydro-naphthyl, indanyl, and biphenyl.Where an aryl substituent is bicyclic and one ring is non-aromatic, itis understood that attachment is to the aromatic ring. An aryl may besubstituted or unsubstituted.

The term “heteroaryl” as used herein refers to any stable monocyclic,bicyclic, or polycyclic carbon ring system of from 4 to 12 atoms in eachring, wherein at least one ring is aromatic and contains from 1 to 4heteroatoms selected from oxygen, nitrogen and sulfur. Phosphorous andselenium may be a heteroatom. Some examples of a heteroaryl includeacridinyl, quinoxalinyl, pyrazolyl, indolyl, benzotriazolyl, furanyl,thienyl, benzothienyl, benzofuranyl, quinolinyl, isoquinolinyl,oxazolyl, isoxazolyl, pyrazinyl, pyridazinyl, pyridinyl, pyrimidinyl,pyrrolyl, and tetrahydroquinolinyl. A heteroaryl includes the N-oxidederivative of a nitrogen-containing heteroaryl.

The term “heterocycle” or “heterocyclyl” as used herein refers to anaromatic or nonaromatic ring system of from five to twenty-two atoms,wherein from 1 to 4 of the ring atoms are heteroatoms selected fromoxygen, nitrogen, and sulfur. Phosphorous and selenium may be aheteroatom. Thus, a heterocycle may be a heteroaryl or a dihydro ortetrathydro version thereof.

The term “aroyl” as used herein refers to an aryl radical derived froman aromatic carboxylic acid, such as a substituted benzoic acid. Theterm “aralkyl” as used herein refers to an aryl group bonded to an alkylgroup, for example, a benzyl group.

The term “carboxyl” as used herein represents a group of the formula—C(═O)OH or —C(═O)O⁻. The terms “carbonyl” and “acyl” as used hereinrefer to a group in which an oxygen atom is double-bonded to a carbonatom >C═O. The term “hydroxyl” as used herein refers to —OH or —O⁻. Theterm “nitrile” or “cyano” as used herein refers to —CN. The term“halogen” or “halo” refers to fluoro (—F), chloro (—Cl), bromo (—Br),and iodo (—I).

The term “substituted” as used herein refers to an atom having one ormore substitutions or substituents which can be the same or differentand may include a hydrogen substituent. Thus, the terms alkyl,cycloalkyl, alkenyl, alkynyl, alkoxy, alkanoyl, alkanoyloxy, alkylamino,alkylaminoalkyl, aryl, heteroaryl, heterocycle, aroyl, and aralkyl asused herein refer to groups which include substituted variations.Substituted variations include linear, branched, and cyclic variations,and groups having a substituent or substituents replacing one or morehydrogens attached to any carbon atom of the group. Substituents thatmay be attached to a carbon atom of the group include alkyl, cycloalkyl,alkenyl, alkynyl, alkoxy, alkanoyl, alkanoyloxy, alkylamino,alkylaminoalkyl, aryl, heteroaryl, heterocycle, aroyl, aralkyl, acyl,hydroxyl, cyano, halo, haloalkyl, amino, aminoacyl, alkylaminoacyl,acyloxy, aryloxy, aryloxyalkyl, mercapto, nitro, carbamyl, carbamoyl,and heterocycle. For example, the term ethyl includes without limitation—CH₂CH₃, —CHFCH₃, —CF₂CH₃, —CHFCH₂F, —CHFCHF₂, —CHFCF₃, —CF₂CH₂F,—CF₂CHF₂, —CF₂CF₃, and other variations as described above. In general,a substituent may itself be further substituted with any atom or groupof atoms.

Some examples of a substituent for a substituted alkyl include halogen,hydroxyl, carbonyl, carboxyl, ester, aldehyde, carboxylate, formyl,ketone, thiocarbonyl, thioester, thioacetate, thioformate,selenocarbonyl, selenoester, selenoacetate, selenoformate, alkoxyl,phosphoryl, phosphonate, phosphinate, amino, amido, amidine, imino,cyano, nitro, azido, carbamato, sulfhydryl, alkylthio, sulfate,sulfonate, sulfamoyl, sulfonamido, sulfonyl, silyl, heterocyclyl, aryl,aralkyl, aromatic, and heteroaryl.

It will be understood that “substitution” or “substituted with” refersto such substitution that is in accordance with permitted valence of thesubstituted atom and the substituent. As used herein, the term“substituted” includes all permissible substituents.

In general, a compound may contain one or more chiral centers. Compoundscontaining one or more chiral centers may include those described as an“isomer,” a “stereoisomer,” a “diastereomer,” an “enantiomer,” an“optical isomer,” or as a “racemic mixture.” Conventions forstereochemical nomenclature, for example the stereoisomer naming rulesof Cahn, Ingold and Prelog, as well as methods for the determination ofstereochemistry and the separation of stereoisomers are known in theart. See, for example, Michael B. Smith and Jerry March, March'sAdvanced Organic Chemistry, 5th edition, 2001. The compounds andstructures of this disclosure are meant to encompass all possibleisomers, stereoisomers, diastereomers, enantiomers, and/or opticalisomers that would be understood to exist for the specified compound orstructure, including any mixture, racemic or otherwise, thereof.

This invention encompasses any and all tautomeric, solvated orunsolvated, hydrated or unhydrated forms, as well as any atom isotopeforms of the compounds and compositions disclosed herein.

This invention encompasses any and all crystalline polymorphs ordifferent crystalline forms of the compounds and compositions disclosedherein.

Additional Embodiments

All publications, references, patents, patent publications and patentapplications cited herein are each hereby specifically incorporated byreference in their entirety for all purposes.

While this invention has been described in relation to certainembodiments, aspects, or variations, and many details have been setforth for purposes of illustration, it will be apparent to those skilledin the art that this invention includes additional embodiments, aspects,or variations, and that some of the details described herein may bevaried considerably without departing from this invention. Thisinvention includes such additional embodiments, aspects, and variations,and any modifications and equivalents thereof. In particular, thisinvention includes any combination of the features, terms, or elementsof the various illustrative components and examples.

The use herein of the terms “a,” “an,” “the” and similar terms indescribing the invention, and in the claims, are to be construed toinclude both the singular and the plural.

The terms “comprising,” “having,” “include,” “including” and“containing” are to be construed as open-ended terms which mean, forexample, “including, but not limited to.” Thus, terms such as“comprising,” “having,” “include,” “including” and “containing” are tobe construed as being inclusive, not exclusive.

Recitation of a range of values herein refers individually to each andany separate value falling within the range as if it were individuallyrecited herein, whether or not some of the values within the range areexpressly recited. For example, the range “4 to 12” includes withoutlimitation any whole, integer, fractional, or rational value greaterthan or equal to 4 and less than or equal to 12, as would be understoodby those skilled in the art. Specific values employed herein will beunderstood as exemplary and not to limit the scope of the invention.

Recitation of a range of a number of atoms herein refers individually toeach and any separate value falling within the range as if it wereindividually recited herein, whether or not some of the values withinthe range are expressly recited. For example, the term “C1-8” includeswithout limitation the species C1, C2, C3, C4, C5, C6, C7, and C8.

Definitions of technical terms provided herein should be construed toinclude without recitation those meanings associated with these termsknown to those skilled in the art, and are not intended to limit thescope of the invention. Definitions of technical terms provided hereinshall be construed to dominate over alternative definitions in the artor definitions which become incorporated herein by reference to theextent that the alternative definitions conflict with the definitionprovided herein.

The examples given herein, and the exemplary language used herein aresolely for the purpose of illustration, and are not intended to limitthe scope of the invention. All examples and lists of examples areunderstood to be non-limiting.

When a list of examples is given, such as a list of compounds, moleculesor compositions suitable for this invention, it will be apparent tothose skilled in the art that mixtures of the listed compounds,molecules or compositions may also be suitable.

EXAMPLES

Thermogravimetric analysis (TGA) was performed using a Q50Thermogravimetric Analyzer (TA Instruments, New Castle, Del.). NMR datawere recorded using a Varian 400 MHz spectrometer.

Example 1 Preparation of Polymeric Precursor Compounds and Compositions

An MPP-CAIGAS polymeric precursor represented by the formula{Cu_(0.7)Ag_(0.25) (Se^(s)Bu)_(3.95)In_(0.3)Ga_(0.4)Al_(0.3)} wassynthesized using the following procedure.

In an inert atmosphere glovebox, a Schlenk tube was charged with 0.31 g(0.6 mmol) of In(Se^(s)Bu)₃, 0.38 g (0.8 mmol) of Ga(Se^(s)Bu)₃, 0.26 g(0.6 mmol) of Al(Se^(s)Bu)₃, 0.28 g (1.4 mmol) of CuSe^(s)Bu and 0.12 g(0.5 mmol) of AgSe^(s)Bu. Benzene (30 mL) was added, and the reactionmixture was stirred at 25° C. for 12 hr. A light yellow solution wasobtained. The solvent was removed under reduced pressure and pentane (30mL) was used to extract the product. The resulting solution was filteredthrough a filter cannula and the volatiles were subsequently removedunder reduced pressure. 1.26 g (93%) of yellow oil was obtained.

Elemental analysis: C, 26.7, H, 5.07. NMR: (1H) 1.06 (br), 1.80 (br),2.12 (br), 3.75 (br) in C₆D₆.

As shown in FIG. 8, the TGA for this MPP-CAIGAS polymeric precursorshowed a transition beginning at about 162° C., having a midpoint atabout 213° C., and ending at about 230° C. The yield for the transitionwas 41.8% (w/w), as compared to a theoretical yield for the formulaCu_(0.7)Ag_(0.25)In_(0.3)Ga_(0.4)Al_(0.3)Se₂ of 44.2% (w/w). Thus, theTGA showed that this polymeric precursor can be used to prepareCu_(0.7)Ag_(0.25)In_(0.3)Ga_(0.4)Al_(0.3)Se₂ layers and materials, andcan be used as a component to prepare other semiconductor layers,crystals, and materials.

Example 2

An MPP-CAGAS polymeric precursor represented by the formula{Ga_(0.5)Al_(0.5)(Se^(s)Bu)_(3.9)Cu_(0.5)Ag_(0.4)} was synthesized usingthe following procedure.

In an inert atmosphere glovebox, a Schlenk tube was charged with 0.48 g(1.0 mmol) of Ga(Se^(s)Bu)₃, 0.44 g (1.0 mmol) of Al(Se^(s)Bu)₃, 0.20 g(1.0 mmol) of CuSe^(s)Bu and 0.20 g (0.8 mmol) of Ag(Se^(s)Bu)₃. Benzene(30 mL) was added, and the reaction mixture was stirred at 25° C. for 12hr. A brown solution was obtained. The solvent was removed and pentane(30 mL) was used to extract the product. The resulting solution wasfiltered through a filter cannula and the volatiles were subsequentlyremoved under reduced pressure. 1.12 g (85%) of yellow oil wasrecovered.

NMR: (1H) 1.07 (br), 1.81 (br), 2.17 (br), 3.77 (br) in C₆D₆.

As shown in FIG. 9, the TGA for this MPP-CAGAS polymeric precursorshowed a transition beginning at about 61° C., having a midpoint atabout 201° C., and ending at about 236° C. The yield for the transitionwas 43.4% (w/w), as compared to a theoretical yield for the formulaCu_(0.5)Ag_(0.4)Ga_(0.5)Al_(0.5)Se₂ of 43.0% (w/w). Thus, the TGA showedthat this polymeric precursor can be used to prepareCu_(0.5)Ag_(0.4)Ga_(0.5)Al_(0.5)Se₂ layers and materials, and can beused as a component to prepare other semiconductor layers, crystals, andmaterials.

Example 3

An MPP-CAIAS polymeric precursor represented by the formula{Cu_(0.5)Ag_(0.5)(Se^(s)Bu)₄In_(0.7)Al_(0.3)} was synthesized using thefollowing procedure.

In an inert atmosphere glovebox, a Schlenk tube was charged with 0.37 g(0.7 mmol) of In(Se^(s)Bu)₃, 0.13 g (0.3 mmol) of Al(Se^(s)Bu)₃, 0.10 g(0.5 mmol) of CuSe^(s)Bu and 0.12 g (0.5 mmol) of AgSe^(s)Bu. Benzene(20 mL) was added, and the reaction mixture was stirred at 25° C. for 12hr. A light yellow solution was obtained. The solvent was removed underreduced pressure and pentane (30 mL) was used to extract the product.The resulting solution was filtered through a filter cannula and thevolatiles were then removed under reduced pressure. 0.62 g (86%) ofyellow oil was obtained.

Elemental analysis: C, 23.6, H, 4.82. NMR: (1H) 1.06 (br), 1.81 (br),2.12 (br), 3.73 (br) in C₆D₆.

As shown in FIG. 10, the TGA for this MPP-CAIAS polymeric precursorshowed a transition beginning at about 165° C., having a midpoint atabout 210° C., and ending at about 230° C. The yield for the transitionwas 46.0% (w/w), as compared to a theoretical yield for the formulaCu_(0.5)Ag_(0.5)In_(0.7)Al_(0.3)Se₂ of 46.3% (w/w). Thus, the TGA showedthat this polymeric precursor can be used to prepareCu_(0.5)Ag_(0.5)In_(0.7)Al_(0.3)Se₂ layers and materials, and can beused as a component to prepare other semiconductor layers, crystals, andmaterials.

Example 4

An MPP-CIGAS polymeric precursor represented by the formula{Cu_(0.9)In_(0.5)Ga_(0.25)Al_(0.25)(Se^(s)Bu)_(3.9)} was synthesizedusing the following procedure.

In an inert atmosphere glovebox, a Schlenk tube was charged with 0.52 g(1.0 mmol) of In(Se^(s)Bu)₃, 0.24 g (0.5 mmol) of Ga(Se^(s)Bu)₃, 0.22 g(0.5 mmol) of Al(Se^(s)Bu)₃ and 0.36 g (1.8 mmol) of CuSe^(s)Bu. Benzene(30 mL) was added, and the reaction mixture was stirred at 25° C. for 12hr. A brown solution was obtained. The solvent was removed and pentane(30 mL) was used to extract the product. The resulting solution wasfiltered through a filter cannula and the volatiles were subsequentlyremoved under reduced pressure. 1.21 g (90%) of yellow oil wasrecovered.

NMR: (1H) 1.00 (br), 1.64 (br), 1.82 (br), 2.03 (br), 3.70 (br) in C₆D₆.

As shown in FIG. 11, the TGA for this MPP-CIGAS polymeric precursorshowed a transition beginning at about 119° C., having a midpoint atabout 218° C., and ending at about 235° C. The yield for the transitionwas 44.4% (w/w), as compared to a theoretical yield for the formulaCu_(0.9)In_(0.5)Ga_(0.25)Al_(0.25)Se₂ of 44.3% (w/w). Thus, the TGAshowed that this polymeric precursor can be used to prepareCu_(0.9)In_(0.5)Ga_(0.25)Al_(0.25)Se₂ layers and materials, and can beused as a component to prepare other semiconductor layers, crystals, andmaterials.

Example 5

An MPP-CAS polymeric precursor represented by the formula{Cu(Se^(s)Bu)₄Al} was synthesized using the following procedure.

In an inert atmosphere glovebox, a Schlenk tube was charged with 0.74 g(1.7 mmol) of Al(Se^(s)Bu)₃ and 0.34 g (1.7 mmol) of CuSe^(s)Bu. Benzene(20 mL) was added, and the reaction mixture was stirred at 25° C. for 12hr. A light yellow solution was obtained. The solvent was removed underreduced pressure and pentane (30 mL) was used to extract the product.The resulting solution was filtered through a filter cannula and thevolatiles were removed under reduced pressure. 0.99 g (92%) of yellowsolid was obtained.

Elemental analysis: C, 28.4, H, 5.49. NMR: (1H) 1.04 (br), 1.70 (br),1.82 (br), 2.03 (br), 2.20 (br), 3.76 (br) in C₆D₆.

As shown in FIG. 12, the TGA for this MPP-CAS polymeric precursor showeda transition beginning at about 60° C., and ending at about 200° C. Theyield for the transition was 39.7% (w/w), as compared to a theoreticalyield for the formula CuAlSe₂ of 39.2% (w/w). Thus, the TGA showed thatthis polymeric precursor can be used to prepare CuAlSe₂ layers andmaterials, and can be used as a component to prepare other semiconductorlayers, crystals, and materials.

Example 6

An MPP-CGAS polymeric precursor represented by the formula{Cu_(0.9)(Se^(s)Bu)_(3.9)Ga_(0.7)Al_(0.3)} was synthesized using thefollowing procedure.

In an inert atmosphere glovebox, a Schlenk tube was charged with 0.33 g(0.7 mmol) of Ga(Se^(s)Bu)₃, 0.13 g (0.3 mmol) of Al(Se^(s)Bu)₃ and 0.18g (0.9 mmol) of CuSe^(s)Bu. Benzene (15 mL) was added, and the reactionmixture was stirred at 25° C. for 12 hr. A light yellow solution wasobtained. The solvent was removed under reduced pressure and pentane (30mL) was used to extract the product. The resulting solution was filteredthrough a filter cannula and the solvent was subsequently removed underreduced pressure. 0.55 g (86%) of yellow oil was obtained.

Elemental analysis: C, 28.7, H, 5.42. NMR: (1H) 1.00 (br), 1.32 (br),1.81 (br), 2.01 (br), 3.72 (br) in C₆D₆.

As shown in FIG. 13, the TGA for this MPP-CGAS polymeric precursorshowed a transition beginning at about 155° C., having a midpoint atabout 210° C., and ending at about 250° C. The yield for the transitionwas 41.0% (w/w), as compared to a theoretical yield for the formulaCu_(0.9)Ga_(0.7)Al_(0.3)Se₂ of 42.2% (w/w). Thus, the TGA showed thatthis polymeric precursor can be used to prepareCu_(0.9)Ga_(0.7)Al_(0.3)Se₂ layers and materials, and can be used as acomponent to prepare other semiconductor layers, crystals, andmaterials.

Example 7

An MPP-CIAS polymeric precursor represented by the formula{Cu_(0.9)(Se^(s)Bu)_(3.9)In_(0.8)Al_(0.2)} was synthesized using thefollowing procedure.

In an inert atmosphere glovebox, a Schlenk tube was charged with 0.84 g(1.6 mmol) of In(Se^(s)Bu)₃, 0.17 g (0.4 mmol) of Al(Se^(s)Bu)₃ and 0.36g (1.8 mmol) of CuSe^(s)Bu. Benzene (30 mL) was added, and the reactionmixture was stirred at 25° C. for 12 hr. A light yellow solution wasobtained. The solvent was removed under reduced pressure and pentane (30mL) was used to extract the product. The resulting solution was filteredthrough a filter cannula and the volatiles were then removed underreduced pressure. 0.95 g (70%) of yellow oil was obtained.

Elemental analysis: C, 24.4, H, 4.97. NMR: (1H) 1.02 (br), 1.73 (br),1.80 (br), 2.04 (br), 3.70 (br) in C₆D₆.

As shown in FIG. 14, the TGA for this MPP-CIAS polymeric precursorshowed a transition beginning at about 168° C., having a midpoint atabout 219° C., and ending at about 235° C. The yield for the transitionwas 46.5% (w/w), as compared to a theoretical yield for the formulaCu_(0.9)In_(0.8)Al_(0.2)Se₂ of 45.6% (w/w). Thus, the TGA showed thatthis polymeric precursor can be used to prepareCu_(0.9)In_(0.8)Al_(0.2)Se₂ layers and materials, and can be used as acomponent to prepare other semiconductor layers, crystals, andmaterials.

Example 8

An MPP-AAS polymeric precursor represented by the formula{Ag(Se^(s)Bu)₄Al} was synthesized using the following procedure.

In an inert atmosphere glovebox, a Schlenk tube was charged with 0.44 g(1.0 mmol) of Al(Se^(s)Bu)₃ and 0.24 g (1.0 mmol) of AgSe^(s)Bu. Benzene(15 mL) was added, and the reaction mixture was stirred at 25° C. for 12hr. A light brown solution was obtained. The solvent was removed underreduced pressure and pentane (30 mL) was used to extract the product.The resulting solution was filtered through a filter cannula thevolatiles were then removed under reduced pressure. 0.56 g (82%) of darkbrown solid was recovered.

Elemental analysis: C, 25.7, H, 4.88. NMR: (1H) 1.05 (t, 12H,³J_(HH)=7.6 Hz), 1.77 (d, 12H, ³J_(HH)=6.0 Hz), 1.86 (m, 4H), 2.08 (m,4H), 3.76 (br, 4H) in C₆D₆.

As shown in FIG. 15, the TGA for this MPP-AAS polymeric precursor showeda transition beginning at about 133° C., having a midpoint at about 196°C., and ending at about 220° C. The yield for the transition was 41.4%(w/w), as compared to a theoretical yield for the formula AgAlSe₂ of43.2% (w/w). Thus, the TGA showed that this polymeric precursor can beused to prepare AgAlSe₂ layers and materials, and can be used as acomponent to prepare other semiconductor layers, crystals, andmaterials.

Example 9

An MPP-AIAS polymeric precursor represented by the formula{Ag(Se^(s)Bu)₄In_(0.7)Al_(0.3)} was synthesized using the followingprocedure.

In an inert atmosphere glovebox, a Schlenk tube was charged with 0.37 g(0.7 mmol) of In(Se^(s)Bu)₃, 0.13 g (0.3 mmol) of Al(Se^(s)Bu)₃ and 0.24g (1.0 mmol) of AgSe^(s)Bu. Benzene (15 mL) was added, and the reactionmixture was stirred at 25° C. for 12 hr. A light brown solution wasobtained. The solvent was removed under reduced pressure and pentane (30mL) was used to extract the product. This solution was filtered througha filter cannula and the volatiles were subsequently removed underreduced pressure. 0.59 g (80%) of yellow oil was obtained.

NMR: (1H) 1.07 (t, 12H, ³J_(HH)=6.4 Hz), 1.81 (d, 12H, ³J_(HH)=6.8 Hz),1.87 (m, 4H), 2.12 (m, 4H), 3.76 (br, 4H) in C₆D₆.

As shown in FIG. 16, the TGA for this MPP-AIAS polymeric precursor. TheTGA showed a transition beginning at about 139° C., having a midpoint atabout 200° C., and ending at about 230° C. The yield for the transitionwas 50.3% (w/w), as compared to a theoretical yield for the formulaAgIn_(0.7)Al_(0.3)Se₂ of 47.9% (w/w). Thus, the TGA showed that thispolymeric precursor can be used to prepare AgIn_(0.7)Al_(0.3)Se₂ layersand materials, and can be used as a component to prepare othersemiconductor layers, crystals, and materials.

Example 10 Preparation of Monomer Compounds

A monomer compound represented by the formula Ga(Se^(n)Bu)₃ wassynthesized using the following procedure.

To a 500-mL round bottom Schlenk flask in an inert atmosphere glove boxwas added NaSe^(n)Bu (28 g, 176 mmol) and THF (200 mL). The flask wasthen transferred to a Schlenk line and a solution of GaCl₃ (10.3 g, 59mmol) in 20 mL of benzene was then added. The reaction mixture wasstirred for 12 h and the volatiles were removed under reduced pressure.The residue was extracted with toluene and filtered. The volatiles fromthe filtrate were then removed under reduced pressure leaving acolorless oil (23 g, 48 mmol, 83% yield).

NMR: (1H; C6D6): 0.85 (t, J_(HH)=7.2 Hz, 9H, CH₃); 1.40 (m, 6H, —CH₂—);1.77 (m, 6H, —CH₂—); 3.03 (br s, 6H, SeCH₂—).

Example 11

A monomer compound represented by the formula In(Se^(n)Bu)₃ wassynthesized using the following procedure.

To a 500-mL round bottom Schlenk flask in an inert atmosphere glove boxwas added InCl₃ (6.95 g, 31 mmol), NaSe^(n)Bu (15 g, 94 mmol), and THF(200 mL). The reaction mixture was transferred to a Schlenk line andstirred for 12 h. The volatiles were subsequently removed under reducedpressure. The remaining solid residue was dissolved in hot toluene andfiltered. The volatiles from the filtrate were removed under reducedpressure and the resulting solid was washed with pentane. The finalcolorless solid was dried under reduced pressure and isolated (15 g, 29mmol, 92% yield).

NMR: (1H; C6D6): 0.913 (t, J_(HH)=7.2 Hz, 9H, CH₃); 1.43 (m, 6H, —CH₂—);1.72 (m, 6H, —CH₂—); 2.90 (t, J_(HH)=7.2 Hz, 6H, SeCH₂—).

Example 12

A monomer compound represented by the formula Ag(Se^(t)Bu) wassynthesized using the following procedure.

^(t)BuSeH (5.8 mmol) and Et₃N (1.1 mL) were slowly added to a solutionof AgNO₃ (1.0 g, 5.8 mmol) in CH₃CN (20 mL) at 0° C. A colorlesssolution with light yellow precipitate formed rapidly. The reactionmixture was allowed to warm to 25° C. and stirred for 12 h. The excess^(t)BuSeH was removed under dynamic vacuum and a grey solid wasrecovered. The solid was washed with CH₃CN (2×100 mL) to afford a greysolid (1.23 g, 87%).

NMR: (1H; CDCl₃): 1.73 (in presence of pyridine).

Example 13

A range of polymeric molecular precursors shown in Table 2 weresynthesized in an inert atmosphere according to the following generalprocedure. A Schlenk tube was charged in an inert atmosphere gloveboxwith M^(B)(ER)₃ and Cu(ER). A solvent, typically toluene or benzene, wasthen added. The Schlenk tube was transferred to a Schlenk line and thereaction mixture was stirred at 25° C. for 1 h. In some cases, thereaction mixture was stirred at about 80° C. for up to 12 h. The solventwas removed under reduced pressure and the product was extracted withpentane. The pentane extract was filtered and the solvent was removedunder reduced pressure to afford a yellow to yellow-orange product. Theproducts ranged from being an oil, to being a semi-solid, to being asolid. Yields of 90% or greater were typical.

TABLE 2 Examples of polymeric molecular precursors TGA PolymericMolecular Precursor Material Target Yield % Target %{Ag_(1.0)Al_(1.0)(Se^(s)Bu)₄} Ag_(1.0)Al_(1.0)Se₂ 41.4 43.2{Ag_(1.0)In_(0.7)Al_(0.3)(Se^(s)Bu)₄} Ag_(1.0)In_(0.7)Al_(0.3)Se₂ 50.347.9 {Cu_(0.9)Ga_(0.7)Al_(0.3)(Se^(s)Bu)_(3.9)}Cu_(0.9)Ga_(0.7)Al_(0.3)Se₂ 41.0 42.2 {Cu_(1.0)Al_(1.0)(Se^(s)Bu)₄}Cu_(1.0)Al_(1.0)Se₂ 38.2 39.2{Cu_(0.5)Ag_(0.5)In_(0.7)Al_(0.3)(Se^(s)Bu)₄}Cu_(0.5)Ag_(0.5)In_(0.7)Al_(0.3)Se₂ 46.0 46.3{Cu_(0.7)Ag_(0.25)In_(0.3)Ga_(0.4)Al_(0.3)(Se^(s)Bu)_(3.95)}Cu_(0.7)Ag_(0.25)In_(0.3)Ga_(0.4)Al_(0.3)Se₂ 41.8 44.2{Cu_(0.9)In_(0.8)Al_(0.2)(Se^(s)Bu)_(3.9)} Cu_(0.9)In_(0.8)Al_(0.2)Se₂46.5 45.6 {Cu_(0.9)In_(0.5)Ga_(0.25)Al_(0.25)(Se^(s)Bu)_(3.9)}Cu_(0.9)In_(0.5)Ga_(0.25)Al_(0.25)Se₂ 44.3 44.4{Cu_(0.5)Ag_(0.4)Ga_(0.5)Al_(0.5)(Se^(s)Bu)_(3.9)}Cu_(0.5)Ag_(0.4)Ga_(0.5)Al_(0.5)Se₂ 43.0 43.4

Example 14 Examples of Controlling the Stoichiometry of Materials

FIG. 17 shows results of methods for stoichiometric control of thecomposition of a polymeric precursor embodiment (MPP) of this invention.The x-axis refers to the weight percent of a particular atom, either Al,In or Ga, in the monomer compounds used to prepare the polymericprecursor. The y-axis refers to the weight percent of a particular atomin the precursor compound as synthesized, as determined by the use ofICP. The straight line correlation observed in FIG. 17 for differentpolymeric precursor compounds shows that the stoichiometry of thepolymeric precursor can be precisely controlled by the quantities of themonomers used to make the polymeric precursors. The straight linecorrelation observed in FIG. 17 also shows that methods of thisdisclosure can be used to make precursor compounds of any arbitrarydesired stoichiometry.

Example 15 Polymeric Precursor Ink Compositions

A polymeric precursor ink composition is prepared in a glovebox in aninert atmosphere by dissolving the polymeric precursor of Example 1 inTHF to a concentration of 12% (w/w), and adding 0.1% (w/w) sodiumrelative to copper as NaIn(Se^(s)Bu)₄.

Example 16 Spin Casting Deposition of Polymeric Precursor InkCompositions

A polymeric precursor ink is prepared by mixing the polymeric precursorof Example 1 with xylene (15% polymer content, by weight) in an inertatmosphere glove box. An aliquot (0.3 mL) of the ink solution isfiltered through a 0.2 um PTFE syringe filter and is deposited onto apiece of 1 inch by 1 inch Mo-coated glass substrate in a raster fashion.The substrate is spun at 1200 rpm for 1 minute using a G3P-8 Spin Coater(Specialty Coating Systems) in an inert atmosphere glove box, and isallowed to sit for about 2 minutes, and placed in a pre-heated (300° C.)furnace for 30 minutes for conversion of the polymer to a CAIGASmaterial. This deposition process (filter/deposit/convert) is repeatedseveral times, and the final deposition and conversion is followed byannealing in a furnace at 550° C. for 1 hour. The CAIGAS film has athickness of about 850 nm.

Example 17 Rod Coating Deposition of Polymeric Precursor InkCompositions

A polymeric precursor ink composition is prepared in a glovebox in aninert atmosphere by dissolving the polymeric precursor of Example 2 inTHF to a concentration of 12% (w/w), and adding 0.1% (w/w) sodiumrelative to copper as NaIn(Se^(s)Bu)₄. The ink is rod coated onto amolybdenum-coated glass substrate using a K CONTROL COATER MODEL 201 (RK Print-Coat Instr., Litlington, UK) in a glovebox in an inertatmosphere.

The substrate is removed and is heated at a temperature of 350° C. in aninert atmosphere. A thin film material is produced which is aphotovoltaic absorber layer. The final film thickness is 1 micron.

Example 18 Dip Coating Deposition of Polymeric Precursor InkCompositions

A polymeric precursor ink composition is prepared in a glovebox in aninert atmosphere by dissolving the polymeric precursor of Example 3 indecane to a total concentration of 20% (w/w). The ink is dip coated ontoan aluminum substrate in an inert atmosphere.

The substrate is removed and is heated at a temperature of 340° C. in aninert atmosphere A thin film material is produced which is aphotovoltaic absorber layer. The final film thickness is 2.5 micron.

Example 19 Slot Die Coating Deposition of Polymeric Precursor InkCompositions

A polymeric precursor ink composition is prepared in a glovebox in aninert atmosphere by dissolving the polymeric precursor of Example 4 inTHF to a concentration of 12% (w/w), and adding 0.1% (w/w) sodiumrelative to copper as NaIn(Se^(s)Bu)₄. The ink is slot die coated onto aMo-coated glass substrate in an inert atmosphere.

The substrate is removed and is heated at a temperature of 300° C. in aninert atmosphere A thin film material is produced which is aphotovoltaic absorber layer. The final film thickness is 1.5 micron.

Example 20

A polymeric precursor ink composition is prepared in a glovebox in aninert atmosphere by dissolving the polymeric precursor of Example 5 in atoluene solution at 20% (w/w). To this solution is added 0.05% (w/w)sodium relative to copper as NaIn(Se^(s)Bu)₄. The ink is slot die coatedonto a molybdenum-coated stainless steel substrate in an inertatmosphere.

The substrate is removed and is heated at a temperature of 380° C. in aninert atmosphere A thin film material is produced which is aphotovoltaic absorber layer. The final film thickness is 2.0 micron.

Example 21 Screen Printing Deposition of Polymeric Precursor InkCompositions

A polymeric precursor ink composition is prepared in a glovebox in aninert atmosphere by dissolving the polymeric precursor of Example 6 indecane to a total concentration of 50% (w/w). The polymeric precursorink is screen printed onto a molybdenum-coated stainless steel substratein an inert atmosphere.

The substrate is removed and is heated at a temperature of 400° C. in aninert atmosphere. A thin film material is produced which is aphotovoltaic absorber layer. The final film thickness is 2.8 micron.

Example 22 Printing Polymeric Precursor Ink Compositions

A polymeric precursor ink is prepared by mixing the polymeric precursorof Example 7 with xylene (1% polymer content, by weight) in an inertatmosphere glove box. The ink is printed onto a molybdenum-coatedstainless steel substrate using an M3D Aerosol Jet Deposition System(Optomec, Albuquerque) in a glovebox in an inert atmosphere.

The substrate is removed and is heated at a temperature of 375° C. in aninert atmosphere. A thin film material is produced which is aphotovoltaic absorber layer. The final film thickness is 500 nm.

Example 23 Spray Pyrolysis Deposition of Polymeric Precursor InkCompositions

A polymeric precursor ink composition is prepared in a glovebox in aninert atmosphere by dissolving the polymeric precursor of Example 1 incyclohexanone to a concentration of 5% (w/w), and adding 0.1% (w/w)sodium relative to copper as NaIn(Se^(s)Bu)₄. The ink is sprayed onto analuminum substrate using a spray pyrolysis unit in a glovebox in aninert atmosphere, the spray pyrolysis unit having an ultrasonicnebulizer, precision flow meters for inert gas carrier, and a tubularquartz reactor in a furnace.

The spray-coated substrate is heated at a temperature of 350° C. in aninert atmosphere. A thin film material is produced which is aphotovoltaic absorber layer. The final film thickness is 2 micron.

Example 24 Preparation of a Solar Cell

A solar cell is made by depositing an electrode layer on a polyethyleneterephthalate substrate.

A thin film material photovoltaic absorber layer is coated onto theelectrode layer according to the following procedure. A polymericprecursor ink composition is prepared in a glovebox in an inertatmosphere by dissolving the polymeric precursor of Example 1 in THF toa concentration of 12% (w/w), and adding 0.1% (w/w) sodium relative tocopper as NaIn(Se^(s)Bu)₄. The ink is slot die coated onto a Mo-coatedglass substrate in an inert atmosphere. The substrate is removed and isheated at a temperature of 300° C. in an inert atmosphere A thin filmmaterial is produced which is a photovoltaic absorber layer. The finalfilm thickness is 1.5 micron.

A CdS window layer is deposited on the absorber layer. An aluminum-dopedZnO TCO layer is deposited onto the window layer.

1. A method for making a precursor compound comprising: a) providingmonomer compounds M^(B1)(ER)₃, M^(B2)(ER)₃, M^(B3)(ER)₃, M^(A1)(ER) andM^(A2)(ER); and b) contacting the monomer compounds; wherein M^(B1) isIn, M^(B2) is Ga, M^(B3) is Al, M^(A1) is Cu, and M^(A2) is Ag, each Eis S, Se, or Te, and each R is independently selected, for eachoccurrence, from alkyl, aryl, heteroaryl, alkenyl, amido, silyl, andinorganic and organic ligands.
 2. The method of claim 1, wherein M^(A1)and M^(A2) are both Cu, or M^(A1) and M^(A2) are both Ag.
 3. The methodof claim 1, wherein the compound is a CA(I,G,A)S, CAIGAS, A(I,G,A)S,AIGAS, C(I,G,A)S, or CIGAS precursor compound.
 4. The method of claim 1,wherein the compound is deficient or enriched in a Group 11 atom.
 5. Acompound made by a process comprising reacting monomers M^(B1)(ER)₃,M^(B2)(ER)₃, M^(B3) (ER)₃ M^(A1)(ER) and M^(A2)(ER), wherein M^(B1) isIn, M^(B2) is Ga, M^(B3) is Al, M^(A1) is Cu, and M^(A2) is Ag, each Eis S, Se, or Te, and R is independently selected, for each occurrence,from alkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganic andorganic ligands.
 6. The compound of claim 5, wherein M^(A1) and M^(A2)are both Cu, or M^(A1) and M^(A2) are both Ag.
 7. The compound of claim5, wherein each E is sulfur or selenium.
 8. The compound of claim 5,wherein the compound is a CA(I,G,A)S, CAIGAS, A(I,G,A)S, AIGAS,C(I,G,A)S, or CIGAS precursor compound.
 9. The compound of claim 5,wherein the compound has the empirical formula(Cu_(1−x)Ag_(x))_(u)(In_(1−y−t)Ga_(y)Al_(t))_(v)((S_(1−z)Se_(z))R)_(w),wherein x is from 0 to 1, y is from 0 to 1, t is from 0.001 to 1, thesum of y plus t is from 0.001 to 1, z is from 0 to 1, u is from 0.5 to1.5, v is from 0.5 to 1.5, w is from 2 to 6, and R represents R groups,of which there are w in number, which are independently selected fromalkyl, aryl, heteroaryl, alkenyl, amido, silyl, and inorganic andorganic ligands.
 10. The compound of claim 9, wherein x is from 0 to0.5, y is from 0 to 1, t is from 0 to 1, the sum of y plus t is from 0to 1, z is from 0 to 1, u is from 0.7 to 1.1, v is from 0.9 to 1.2, andw is from 2 to
 6. 11. The compound of claim 9, wherein x is from 0 to0.3, y is from 0 to 1, t is from 0 to 1, the sum of y plus t is from 0to 1, z is from 0 to 1, u is from 0.7 to 1.1, v is 1, and w is from 3 to5.
 12. The compound of claim 9, wherein x is from 0 to 0.2, y is from 0to 1, t is from 0 to 1, the sum of y plus t is from 0 to 1, z is from 0to 1, u is from 0.7 to 1.1, v is 1, and w is from 3.5 to 4.5.
 13. Thecompound of claim 5, wherein the compound is deficient in a Group 11atom.
 14. The compound of claim 5, wherein the compound is linear,branched, cyclic, an alternating copolymer, a block copolymer, a randomcopolymer, or a mixture of any of the foregoing.
 15. The compound ofclaim 5, wherein each R is independently selected, for each occurrence,from (C1-8)alkyl.
 16. The compound of claim 5, wherein each R isindependently selected, for each occurrence, from (C1-4)alkyl.
 17. Thecompound of claim 5, wherein the compound is an oil at a temperaturebelow about 100° C.
 18. The compound of claim 5, further comprisingthree or more repeating units {M^(B)(ER)(ER)}, or three or morerepeating units {M^(A)(ER)(ER)}.
 19. The compound of claim 5, whereinthe compound has any one of the formulas: (RE)₂-BB(AB)_(n),(RE)₂-B(AB)_(n)B, (RE)₂-B(AB)_(n)B(AB)_(m), (RE)₂-(BA)_(n)BB,(RE)₂-B(BA)_(n)B, (RE)₂-(BA)_(n)B(BA)_(m)B, ^(cyclic)(AB)_(n),^(cyclic)(BA)_(n), (RE)₂-(BB)(AABB)_(n), (RE)₂-(BB)(AABB)_(n)(AB)_(m),(RE)₂-(B)(AABB)_(n)(B)(AB)_(m), (RE)₂-[B(AB)_(n)]⁻, (RE)₂-[(BA)_(n)B]⁻,

(RE)₂-BB(AB¹)_(n)(AB²)_(m), (RE)₂-BB(AB¹)_(n)(AB²)_(m)(AB¹)_(p),(RE)₂-BB (AB¹)_(n)(AB²)_(m)(AB¹)_(p), (RE)₂-BB(A¹B)_(n)(A²B)_(m),(RE)₂-BB(A¹B)_(n)(A²B)_(m)(A¹B)_(p), and a mixture of any of theforegoing, wherein A is the repeat unit {M^(A)(ER)(ER)}, B is the repeatunit {M^(B)(ER)(ER)}, p is one or more, n is one or more, and m is oneor more.
 20. The compound of claim 5, wherein the compound has any oneof the repeat unit formulas:{Cu_(0.7)Ag_(0.25)(Se^(s)Bu)_(3.95)In_(0.3)Ga_(0.4)Al_(0.3)},{Ga_(0.5)Al_(0.5)(Se^(s)Bu)_(3.9)Cu_(0.5)Ag_(0.4)},{Cu_(0.5)Ag_(0.5)(Se^(s)Bu)₄In_(0.7)Al_(0.3)},{Cu_(0.9)In_(0.5)Ga_(0.25)Al_(0.25)(Se^(s)Bu)_(3.9)},{Cu_(0.5)(Se^(s)Bu)₄Al}, {Cu_(0.9)(Se^(s)Bu)_(3.9)Ga_(0.7)Ag_(0.3)},{Cu_(0.9)(Se^(s)Bu)_(3.9)In_(0.8)Al_(0.2)}, {Ag(Se^(s)Bu)₄Al},{Ag(Se^(s)Bu)₄In_(0.7)Al_(0.3)},{Cu_(0.5)Ag_(0.5)(Se^(s)Bu)₄(In,Ga,Al)},{Cu_(0.7)Ag_(0.1)(Se^(s)Bu)_(3.8)Ga_(0.2)In_(0.7)Al_(0.1)},{Cu_(0.8)Ag_(0.2)(Se^(s)Bu)₄(In,Ga,Al)},{Cu_(0.2)Ag_(0.8)(Se^(s)Bu)₄(In,Ga,Al)},{Cu_(0.5)Ag_(0.5)(Se^(s)Bu)₄Ga_(0.45)In_(0.8)Al_(0.05)},{Cu_(0.85)Ag_(0.1)(Se^(s)Bu)_(3.95)Ga_(0.15)In_(0.7)Al_(0.15)},{Cu_(0.5)Ag_(0.5)(Se^(s)Bu)₄Ga_(0.3)In_(0.7)Al_(0.01)},{Cu_(0.8)Ag_(0.05)(Se^(s)Bu)_(3.85)Ga_(0.3)In_(0.3)Al_(0.4)},{(Cu,Ag)(Se^(t)Bu)(Se^(n)Bu)(In,Ga,Al)(Se^(n)Bu)₂},{(Cu,Ag)(S^(t)Bu)(S^(i)Pr)(In,Ga,Al)(S^(i)Pr)₂},{Cu_(1.40)Ag_(0.10)(Se^(t)Bu)_(1.5)(Se^(n)Bu)(In_(0.7)Ga_(0.25)Al_(0.05))(Se^(n)Bu)₂};{Cu_(1.30)Ag_(0.10)(S^(t)Bu)_(1.4)(S^(t)Bu)(In_(0.85)Ga_(0.1)Al_(0.05))(S^(t)Bu)₂};{Cu_(1.20)Ag_(0.10)(S^(t)Bu)_(1.3)(S^(n)Bu)(In_(0.80)Ga_(0.15)Al_(0.05))(S^(n)Bu)₂};{Cu_(1.10)Ag_(0.10)(Se^(t)Bu)_(1.2)(Se^(n)Bu)(In_(0.75)Ga_(0.20)Al_(0.05))(Se^(n)Bu)₂};{Cu_(1.05)Ag_(0.05)(S^(t)Bu)_(1.1)(Se^(t)Bu)(In_(0.7)Ga_(0.2)Al_(0.1))(Se^(t)Bu)₂};{Cu_(0.90)Ag_(0.10)(S^(t)Bu)(Se^(n)Bu)(In_(0.7)Ga_(0.25)Al_(0.05))(Se^(n)Bu)₂};{Cu_(0.85)Ag_(0.10)(S^(t)Bu)_(0.95)(S^(t)Bu)(In_(0.85)Ga_(0.1)Al_(0.05))(S^(t)Bu)₂};{Cu_(0.80)Ag_(0.20)(S^(t)Bu)(S^(n)Bu)(In_(0.80)Ga_(0.15)Al_(0.05))(S^(n)Bu)₂};{Cu_(0.75)Ag_(0.20)(Se^(t)Bu)_(0.95)(Se^(n)Bu)(In_(0.75)Ga_(0.20)Al_(0.05))(Se^(n)Bu)₂};{Cu_(0.70)Ag_(0.30)(S^(t)Bu)(Se^(t)Bu)(In_(0.7)Ga_(0.2)Al_(0.1))(S^(t)Bu)₂};{Cu_(0.65)Ag_(0.30)(Se^(t)Bu)_(0.95)(S^(t)Bu)(In_(0.6)Ga_(0.3)Al_(0.1))(S^(t)Bu)₂};{Cu_(0.60)Ag_(0.40)(Se^(t)Bu)₂(In_(0.5)Ga_(0.4)Al_(0.1))(Se^(t)Bu)₂};{Cu_(0.50)Ag_(0.50)(Se^(t)Bu)(Se^(n)Bu)(In_(0.5)Ga_(0.4)Al_(0.1))(Se^(n)Bu)₂};{Cu_(0.30)Ag_(0.65)(S^(t)Bu)_(0.95)(S^(t)Bu)(In_(0.5)Ga_(0.5)Al_(0.1))(S^(t)Bu)₂};{Cu_(0.30)Ag_(0.70)(S^(t)Bu)(S^(n)Bu)(In_(0.4)Ga_(0.5)Al_(0.1))(Se^(n)Bu)₂};{Cu_(0.20)Ag_(0.75)(Se^(t)Bu)_(0.95)(Se^(n)Bu)(In_(0.4)Ga_(0.5)Al_(0.1))(S^(n)Bu)₂};{Cu_(0.20)Ag_(0.80)(S^(t)Bu)(Se^(t)Bu)(In_(0.3)Ga_(0.1)Al_(0.6))(Se^(t)Bu)₂};{Cu_(0.10)Ag_(0.85)(Se^(t)Bu)_(0.95)(S^(t)Bu)(In_(0.3)Ga_(0.6)Al_(0.1))(S^(t)Bu)₂};{Cu_(0.10)Ag_(0.90)(Se^(t)Bu)₂(In_(0.2)Ga_(0.7)Al_(0.1))(Se^(t)Bu)₂}.